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Sample records for zero-valent iron barrier

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

    PubMed

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

    2002-08-01

    Zero-valent iron (Fe0)-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 Fe0-barrier matrix. The present study was undertaken to evaluate the microbial population and community composition in the reducing zone of influence by Fe0 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 Fe0 environment despite a relatively high pH condition within the Fe0 barrier (up to pH approximately 10). In comparison with those found in the background soil/groundwater samples, the enhanced microbial population ranged from approximately 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 over time, 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 Fe0 barriers are yet to be evaluated. PMID:12194417

  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. 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 ...

  4. 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.

  5. 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 an unusually comprehensive hydrologic characterization so that the design can be based on a thorough understanding of subsurface heterogeneity rather than on average values for hydraulic parameters. Scientists and engineers are capable of conducting the level of investigation required. However, design costs will increase, and the pre-design field work may demonstrate that a passive PRB is not suitable for a particular site. In such cases, an option to consider is hydraulic augmentation, such as pumping (in which the system is no longer passive) or gravity flow from drains. In these circumstances, operation of the treatment media is under known hydraulic conditions. These systems typically contain the treatment media in a vault or in drums. Most of the media problems in such systems have been related to the exclusion of air and can be addressed by better engineering design or by frequent maintenance. Finally, a number of outstanding issues require resolution for further application of this technology. Of particular interest to DOE is resolving the removal mechanisms for uranium and technetium. Few data are available for the latter, and for the former, the technical literature is contradictory. Determining the mechanisms has long-term cost implications; engineers must consider whether it is appropriate to remove or simply abandon a barrier that is no longer functioning. Other issues that are unresolved include determining how hydraulic performance is affected by the emplacement method and quantifying the effects of varying groundwater types on barrier longevity.

  6. Monitoring of Zero-Valent Iron Permeable Reactive Barriers: Electrical Properties and Barrier Aging

    NASA Astrophysics Data System (ADS)

    Labrecque, D. J.; Adkins, P. L.; Slater, L. D.; Versteeg, R.; Sharpe, R.

    2007-12-01

    An innovative method of groundwater remediation invented in the 1990"s, Permeable Reactive Barriers, use sand-sized grains of scrap iron placed in trenches or injected under pressure to remediate a number of organic and inorganic contaminants. Monitoring the aging of these barriers becomes increasingly important as many of these barriers approach their predicted life spans. In-situ resistivity and induced polarization studies have been conducted at six barriers at four different sites: Monticello, Utah; the Denver Federal Center; Kansas City, Missouri; and East Helena, Montana. As some barriers tend to age dramatically faster than others, for this study we consider low permeability barriers as of greater age, as "old" barriers tend to loose permeability rather than exhaust reactive materials. One complicating factor is that two of the barriers studied appear to have issues related to installation. One site, the former Asarco Smelter Site near East Helena, Montana, has been instrumented with an autonomous monitoring system allowing continuous monitoring of the evolution of a relatively new (less than three years old) barrier. The barrier showed surprisingly rapid evolution over the first year of monitoring with changes in both resistivity and chargeability of tens of percent per month. In general, the electrical properties of all of the barriers studied follow a pattern. New barriers are fairly resistive with in-situ conductivity only a few times background (outside the barrier) values. Older barriers get increasingly conductive, with failed barriers showing values of over 100 S/m. The induced polarization response is more complicated. Chargeability values increase over time for young barriers, are largest for healthy barriers in the middle of their lifespan, and decrease as the barrier ages.

  7. 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.

  8. 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...

  9. Zero-valent iron nanoparticles preparation

    SciTech Connect

    Oropeza, S.; Corea, M.; Gmez-Yez, 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. 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.

  11. 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.

  12. 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 ...

  13. 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...

  14. 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...

  15. ZERO-VALENT IRON FOR HIGH-LEVEL ARSENITE REMOVAL

    EPA Science Inventory

    This study conducted by flow through column systems was aimed at investigating the feasibility of using zero-valent iron for arsenic remediation in groundwater. A high concentration arsenic solution (50 mg l-1) was prepared by using sodium arsenite (arsenic (III)) to simulate gr...

  16. 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...

  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. In situ removal of arsenic from groundwater by using permeable reactive barriers of organic matter/limestone/zero-valent iron mixtures.

    PubMed

    Gibert, O; de Pablo, J; Cortina, J-L; Ayora, C

    2010-08-01

    In this study, two mixtures of municipal compost, limestone and, optionally, zero-valent iron were assessed in two column experiments on acid mine treatment. The effluent solution was systematically analysed throughout the experiment and precipitates from both columns were withdrawn for scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffractometry analysis and, from the column containing zero-valent iron, solid digestion and sequential extraction analysis. The results showed that waters were cleaned of arsenic, metals and acidity, but chemical and morphological analysis suggested that metal removal was not due predominantly to biogenic sulphide generation but to pH increase, i.e. metal (oxy)hydroxide and carbonate precipitation. Retained arsenic and metal removal were clearly associated to co-precipitation with and/or sorption on iron and aluminum (oxy)hydroxides. An improvement on the arsenic removal efficiency was achieved when the filling mixture contained zero-valent iron. Values of arsenic concentrations were then always below 10 microg/L. PMID:20387094

  19. 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.

  20. 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 same oil/surfactant membrane used in EZVI. The removal of cadmium and lead from a seawater matrix is a unique challenge. It requires a system that is resistant to the corrosive nature of seawater while removing specific ions that are in a relatively low concentration compared to naturally occurring seawater salts. Laboratory studies conducted show greater than 99% removal of lead and 96% removal of cadmium from a seawater solution spiked at 5 mg/L that was treated with an Emulsified Zero-Valent Metal (EZVM). The cadmium and lead are removed from the solution as they transport across the emulsion membrane and plate out onto the zero-valent metal surface.

  1. 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.

  2. 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.

  3. 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

  4. 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.

  5. 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.

  6. Magnetic memory effect in chelated zero valent iron nanoparticles

    NASA Astrophysics Data System (ADS)

    Ghosh, N.; Mandal, B. K.; Mohan Kumar, K.

    2012-11-01

    We report the study of nonequilibrium magnetic behavior of air stable zero valent iron nanoparticles synthesized in presence of N-cetyl-N,N,N-trimethyl ammonium bromide chelating agent. X-ray photoelectron spectroscopy study has suggested the presence of iron oxides on nZVI surfaces. Zero-field-cooled and field-cooled magnetization measurements have been carried out at 20-300 K and 100 Oe. For field-cooled measurements with 1 h stops at 200, 100 and 50 K when compared with the warming cycle, we found the signature of magnetic memory effect. A study of magnetic relaxation at the same temperatures shows the existence of two relaxation times.

  7. Kinetics of zero valent iron nanoparticle oxidation in oxygenated water.

    PubMed

    Greenlee, Lauren F; Torrey, Jessica D; Amaro, Robert L; Shaw, Justin M

    2012-12-01

    Zero valent iron (ZVI) nanoparticles are versatile in their ability to remove a wide variety of water contaminants, and ZVI-based bimetallic nanoparticles show increased reactivity above that of ZVI alone. ZVI nanoparticles degrade contaminants through the reactive species (e.g., OH*, H(2(g)), H(2)O(2)) that are produced during iron oxidation. Measurement and modeling of aqueous ZVI nanoparticle oxidation kinetics are therefore necessary to optimize nanoparticle design. Stabilized ZVI and iron-nickel nanoparticles of approximately 150 nm in diameter were synthesized through solution chemistry, and nanoparticle oxidation kinetics were determined via measured mass change using a quartz crystal microbalance (QCM). Under flowing aerated water, ZVI nanoparticles had an initial exponential growth behavior indicating surface-dominated oxidation controlled by migration of species (H(2)O and O(2)) to the surface. A region of logarithmic growth followed the exponential growth which, based on the Mott-Cabrera model of thin oxide film growth, suggests a reaction dominated by movement of species (e.g., iron cations and oxygen anions) through the oxide layer. The presence of ethanol or a nickel shell on the ZVI nanoparticles delayed the onset of iron oxidation and reduced the extent of oxidation. In oxygenated water, ZVI nanoparticles oxidized primarily to the iron oxide-hydroxide lepidocrocite. PMID:23130994

  8. 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...

  9. 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 1.0mL/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 300h using 80g/40g 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 20.0mg/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

  10. [Dechlorination of HCB by bimetals based on zero valent iron].

    PubMed

    Zeng, Xian-Wei; Liu, Jian-Guo; Nie, Xiao-Qin

    2013-01-01

    Based on the reducing capacity of zero valent iron, the study investigated the behavior of dechlorination of hexachlorobenzene by bimetals synthetized using Fe with Ag, Pb or Cu as catalysts, respectively. The results showed that bimetals could dechlorinate HCB faster than Fe(0) did, the optimal ratios of Ag/Fe, Pb/Fe and Cu/Fe were 0.2%, 0.5% and 1%. After reacting 2 hours, the dechlorination rates of HCB by Ag/Fe, Pb/Fe and Cu/Fe were 93.5%, 88.5% and 49.6% respectively. The catalyst metal distribution had a great effect on the reductive dechlorination capacity of the bimetal systems, due to more galvanic cells produced by well-distributed catalyst metal and iron. Increasing the amount of bimetal was an effective way to promote HCB dechlorination rate, 88.6% HCB was degraded in 2 h by 0.8 g Pb/Fe while only 38.3% HCB was degraded by 0.1 g Pb/Fe. Besides, HCB dechlorination could be enhanced a little with increasing ionic strength, the HCB dechlorination rates were 93.5%, 98.0% and 98.9% respectively with Na2SO4 concentration at 0, 0.05 and 0.5 mol x L(-1). PMID:23487936

  11. Electrokinetics Enhanced Delivery of Nano-scale Zero Valent Iron

    NASA Astrophysics Data System (ADS)

    Chowdhury, A. I.; O'Carroll, D. M.; Xu, Y.; Sleep, B. E.

    2010-12-01

    Nano-scale zero valent iron (NZVI) has shown promising results for remediation of a wide range of chlorinated hydrocarbons in the subsurface. Although rapid aggregation and subsequent sedimentation limit bare NZVI migration in subsurface systems, surface modifications have improved the colloidal stability of NZVI, enhancing NZVI migration through porous media in lab-scale experiments. However, delivery of NZVI through low permeability soil is still an unresolved challenge. Electrokinetics (EK) has been used extensively in low permeability porous media for the remediation of a variety of hazardous wastes and in particular heavy metals. Since NZVI has a net negative surface charge electrokinetics has been proposed to enhance NZVI transport in the subsurface. However, increased dissolved oxygen and lower pH, due to electrolysis of water at the anode, oxidizes Fe0 particles to Fe2+/Fe3+ and thus affects the remediation potential. This study focuses on minimization of NZVI oxidation and quantification of NZVI migration enhancement due to the EK application. Application of 50 and 100 mA currents delivered 6.0 and 4.8 times more NZVI through coarse sand, respectively, when compared to no EK application. This ratio increased to 21 and 31 at 50 and 100 mA currents when finer sand was used. In addition, a numerical model based on traditional colloidal filtration theory (CFT) fit the experimental results well.

  12. Mechanism study of nitrate reduction by nano zero valent iron.

    PubMed

    Hwang, Yu-Hoon; Kim, Do-Gun; Shin, Hang-Sik

    2011-01-30

    This study investigates the fate of nitrogen species during nitrate reduction by nano-scale zero valent iron (NZVI) and related reaction mechanisms. The NZVI used for the experiments was prepared by chemical reduction without a stabilizing agent. NZVI has great ability to reduce nitrate. However, the question of what end-product results from nitrate reduction by NZVI has sparked controversy. Establishing nitrogen mass balance by quantitative analysis of aqueous phase and gas-phase nitrogen species, this study clearly determines that nitrate was converted to ammonium ion followed by ammonia stripping under a strong alkaline condition, which leads to a decrease in the total aqueous nitrogen amount. Moreover, some of the major reactions, which consisted of nitrate reduction, ammonia production, and ammonia stripping were modelled by pseudo first-order kinetics. According to the model estimation results, additional reaction mechanisms would exist in an early stage of reaction. This might be due to the adsorption and desorption reaction which could be explained by the core-shell structure model. PMID:21093984

  13. 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

  14. 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 ...

  15. 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...

  16. 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...

  17. 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 ...

  18. 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...

  19. 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...

  20. HIGH-LEVEL ARSENITE REMOVAL FROM GROUNDWATER 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...

  1. 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...

  2. 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...

  3. 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 10mM 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...

  4. 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...

  5. 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...

  6. 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...

  7. Effects of Precipitation and Particle Size on Low Frequency Electrical Properties of Zero Valent Iron

    NASA Astrophysics Data System (ADS)

    Wu, Y.; Slater, L.

    2004-12-01

    Observational methods are required to monitor the long-term efficiency of permeable reactive barrier (PRB) installations used to remediate hydrocarbon and heavy metal contaminated groundwater. Our previous studies investigated the relationship between induced polarization (IP) and zero valent iron (Fe0) surface area and electrolyte activity. In this continuous research, we performed experiments on mixtures of Fe0 and Ottawa sand to study (1) the relationship between IP and zero valent iron particle size, and (2) the impact of precipitation induced on the Fe0 surface. The latter experiment addresses the issue of whether reduction in PRB performance can be inferred from electrical measurements. The effect of iron particle size on IP was studied by running background solutions (0.01 ¡C 0.1M NaCl) through samples of the mixture of sand with 5% of different sizes of iron (diameter 1-0.2 mm). Precipitation experiments were conducted by running samples with different solutions to induce precipitation on the iron surface. This involved: (1) long term execution (about 1 year) of four identical samples (5% Fe0 mixture with sand) continuously flushed with four different solutions (0.1 M NaHCO3, 0.1 M Na2SO4, 0.1 M Na2HPO4 and pure water); (2) a short term experiment (in days) with high percentage of Fe0 (30%, 70%) run with high highly basic solutions (0.1M NaOH and 0.1 M Na2CO3). The results show that the IP response is correlated with iron particle size: First, the IP magnitude is inversely proportional to iron particle diameter principally due to the inverse relation between particle diameter and specific surface area. Second, the dominant relaxation time of the polarization is inversely proportional to the particle diameter. The short term precipitation experiment revealed two significant observations: (1) the IP magnitude increased after induced precipitation on Fe0 surface which we tentatively attribute to an increase in the surface area due to an irregular coating of metallic precipitants (FeCO3, Fe(OH)2, FeOOH, Fe(OH)3) on the Fe0 (2) a clear increase in the time constant, which we attribute to an increase in the effective particle size due to the precipitation. Our results to date suggest that IP may be a viable method for long-term monitoring of reactive iron barriers.

  8. 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.

  9. Toxicity of zero-valent iron nanoparticles to a trichloroethylene-degrading groundwater microbial community.

    PubMed

    Zabetakis, Kara M; Nio de Guzmn, Gabriela T; Torrents, Alba; Yarwood, Stephanie

    2015-01-01

    The microbiological impact of zero-valent iron used in the remediation of groundwater was investigated by exposing a trichloroethylene-degrading anaerobic microbial community to two types of iron nanoparticles. Changes in total bacterial and archaeal population numbers were analyzed using qPCR and were compared to results from a blank and negative control to assess for microbial toxicity. Additionally, the results were compared to those of samples exposed to silver nanoparticles and iron filings in an attempt to discern the source of toxicity. Statistical analysis revealed that the three different iron treatments were equally toxic to the total bacteria and archaea populations, as compared with the controls. Conversely, the silver nanoparticles had a limited statistical impact when compared to the controls and increased the microbial populations in some instances. Therefore, the findings suggest that zero-valent iron toxicity does not result from a unique nanoparticle-based effect. PMID:26030685

  10. 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.

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

    NASA Astrophysics Data System (ADS)

    Wu, Yuxin; Versteeg, Roelof; Slater, Lee; LaBrecque, Douglas

    2009-05-01

    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 3 and iron oxides precipitation under simulated field geochemical conditions. We identified CaCO 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 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 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 3 precipitation. Comparison between laboratory and field data shows consistent changes in electrical signatures due to iron corrosion and secondary mineral precipitation.

  12. 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.

  13. 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.

  14. 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...

  15. 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.

  16. The use of zero-valent iron for groundwater remediation and wastewater treatment: a review.

    PubMed

    Fu, Fenglian; Dionysiou, Dionysios D; Liu, Hong

    2014-02-28

    Recent industrial and urban activities have led to elevated concentrations of a wide range of contaminants in groundwater and wastewater, which affect the health of millions of people worldwide. In recent years, the use of zero-valent iron (ZVI) for the treatment of toxic contaminants in groundwater and wastewater has received wide attention and encouraging treatment efficiencies have been documented. This paper gives an overview of the recent advances of ZVI and progress obtained during the groundwater remediation and wastewater treatment utilizing ZVI (including nanoscale zero-valent iron (nZVI)) for the removal of: (a) chlorinated organic compounds, (b) nitroaromatic compounds, (c) arsenic, (d) heavy metals, (e) nitrate, (f) dyes, and (g) phenol. Reaction mechanisms and removal efficiencies were studied and evaluated. It was found that ZVI materials with wide availability have appreciable removal efficiency for several types of contaminants. Concerning ZVI for future research, some suggestions are proposed and conclusions have been drawn. PMID:24457611

  17. 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

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

    EPA Science Inventory

    Large groundwater plumes contaminated with toxic metal ions, including radionuclides, exist at several DOE facilities. Previous research indicated that both zero valent iron and sulfate reducing bacteria can yield significant decreases in concentrations of redox sensitive metals ...

  19. 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...

  20. 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).

  1. 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 barriers 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.

  2. 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

  3. Nitrate removal by entrapped zero-valent iron nanoparticles in calcium alginate.

    PubMed

    Krajangpan, Sita; Bermudez, Juan J Elorza; Bezbaruah, Achintya N; Chisholm, Bret J; Khan, Eakalak

    2008-01-01

    Zero-valent iron nanoparticles (nZVI) were successfully entrapped in calcium alginate beads. The potential use of this technique in environmental remediation using nitrate as a model contaminant was investigated. Kinetics of nitrate degradation using bare nZVI (approximately 35 nm dia) and entrapped nZVI were compared. Calcium alginate beads show promise as the entrapment medium for nZVI for possible use in permeable reactive barriers for groundwater remediation. Based on scanning electron microscopy images it can be inferred that the alginate gel cluster acts as a bridge that binds the nZVI particles together. Kinetic experiments with 100, 60, and 20 mg NO3--N L(-1) indicate that 50-73% nitrate-N removal was achieved with entrapped nZVI as compared to 55-73% with bare nZVI over a 2 h period. The controls ran simultaneously show little or no NO3--N removal. Statistical analysis indicates that there was no significant difference between the reaction rates of bare and entrapped nZVI. The authors have shown for the first time that nZVI can be effectively entrapped in Ca-alginate beads and no significant decrease in the reactivity of nZVI toward the model contaminant (nitrate here) was observed after the entrapment. PMID:19092199

  4. 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, ...

  5. ZERO-VALENT IRON PRB APPLICATION EXPANDS TO ARSENIC REMOVAL

    EPA Science Inventory

    The U.S. EPA Office of Research and Developments 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, ...

  6. 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.

  7. Laboratory evaluation of zero-valent iron to treat water impacted by acid mine drainage.

    PubMed

    Wilkin, Richard T; McNeil, Mary S

    2003-11-01

    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 simulated mine drainage (initial pH 2.3-4.5; total dissolved solids 14000-16000 mgl(-1)). Metal removal from solution and acid-neutralization occurred simultaneously and were most rapid during the initial 24 h of reaction. Reaction half-lives ranged from 1.50+/-0.09 h for Al to 8.15+/-0.36 h for Zn. Geochemical model results indicate that metal removal is most effective in solutions that are highly undersaturated with respect to pure-metal hydroxides suggesting that adsorption is the initial and most rapid metal uptake mechanism. Continued adsorption onto or co-precipitation with iron corrosion products are secondary metal uptake processes. Sulfate green rust was identified as the primary iron corrosion product, which is shown to be the result of elevated [SO(4)(2-)]/[HCO(3)(-)] ratios in solution. Reversibility studies indicate that zero-valent iron will retain metals after shifts in redox states are imposed, but that remobilization of metals may occur after the acid-neutralization capacity of the material is exhausted. PMID:13129511

  8. 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).

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

    PubMed

    Busch, J; Meiner, 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

  10. 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

  11. 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.

  12. 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

  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 municipal water treatment applications. Sulfur-modified iron has been found to not only be an extremely economical treatment technology for municipal water supplies, where very large quantities of water must be treated economically, but it has also been demonstrated to immobilize technetium. It has the added benefit of eliminating several other harmful chemicals in water supplies. These include arsenic and selenium. In one large-scale evaluation study an integrated system implemented chemical reduction of nitrate with sulfur-modified iron followed by filtration for arsenic removal. The sulfur-modified iron that was used was an iron-based granular medium that has been commercially developed for the removal of nitrate, co-contaminants including uranium, vanadium and chromium, and other compounds from water. The independent study concluded that 'It is foreseen that the greatest benefit of this technology (sulfur-modified iron) is that it does not produce a costly brine stream as do the currently accepted nitrate removal technologies of ion exchange and reverse osmosis. This investigation confirmed that nitrate reduction via sulfur-modified iron is independent of the hydraulic loading rate. Future sulfur-modified iron treatment systems can be designed without restriction of the reactor vessel dimensions. Future vessels can be adapted to existing site constraints without being limited to height-to-width ratios that would exist if nitrate reduction were to depend on hydraulic loading rate'. Sulfur-modified iron was studied by the Pacific Northwest National Laboratory (PNNL) for its effectiveness in the reduction and permanent sequestration of technetium. The testing was done using Hanford Site groundwater together with sediment. The report stated, 'Under reducing conditions, TcO{sub 4} is readily reduced to TcIV, which forms highly insoluble oxides such at TcO{sub 2}.nH{sub 2}O. However, (re)oxidation of TcIV oxides can lead to remobilization. Under sulfidogenic conditions, most TcIV will be reduced and immobilized as Tc{sub 2}S{sub 7}, which is less readily re-mobilized, even under oxic conditions. This process should be favored by stimulation of sulfidogenic conditions'. The sulfur-modified iron provides the sulfur, together with the iron, to maintain this stable sequestration of technetium. As a result of these and other studies demonstrating the cost-effectiveness of sulfur-modified iron in treating technetium and other hazardous compounds in Hanford Site groundwater and its cost-effectiveness in reducing nitrate, the Richland Operations Office of the Department of Energy issued a change order to the Central Plateau Contractor providing for the testing of sulfur-modified iron in a mobile pilot unit at the Hanford Site. Further testing is anticipated to produce refinements in operating conditions and further optimization of the existing process. (authors)

  14. 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.

  15. 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.

  16. 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...

  17. 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...

  18. 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.

  19. Microbial reduction of nitrate in the presence of zero-valent iron and biochar.

    PubMed

    Oh, Seok-Young; Seo, Yong-Deuk; Kim, Beomseok; Kim, In Young; Cha, Daniel K

    2016-01-01

    The denitrification of nitrate (NO3(-)) by mixed cultures in the presence of zero-valent iron [Fe(0)] and biochar was investigated through a series of batch experiments. It was hypothesized that biochar may provide microbes with additional electrons to enhance the anaerobic biotransformation of nitrate in the presence of Fe(0) by facilitating electron transfer. When compared to the anaerobic transformation of nitrate by microbes in the presence of Fe(0) alone, the presence of biochar significantly enhanced anaerobic denitrification by microbes with Fe(0). Graphite also promoted the anaerobic microbial transformation of nitrate with Fe(0), and it was speculated that electron-conducting graphene moieties were responsible for the improvement. The results obtained in this work suggest that nitrate can be effectively denitrified by microbes with Fe(0) and biochar in natural and engineered systems. PMID:26600458

  20. Demonstration of combined zero-valent iron and electrical resistance heating for in situ trichloroethene remediation.

    PubMed

    Truex, M J; Macbeth, T W; Vermeul, V R; Fritz, B G; Mendoza, D P; Mackley, R D; Wietsma, T W; Sandberg, G; Powell, T; Powers, J; Pitre, E; Michalsen, M; Ballock-Dixon, S J; Zhong, L; Oostrom, M

    2011-06-15

    The effectiveness of in situ treatment using zero-valent iron (ZVI) for nonaqueous 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 (TCE) source area, combining moderate-temperature subsurface electrical resistance heating with in situ ZVI treatment was shown to accelerate TCE treatment by a factor of about 4 based on organic daughter products and a factor about 8 based on chloride concentrations. A mass-discharge-based analysis was used to evaluate reaction, dissolution, and volatilization processes at ambient groundwater temperature (~10 C) and as temperature was increased up to about 50 C. Increased reaction and contaminant dissolution were observed with increased temperature, but vapor- or aqueous-phase migration of TCE out of the treatment zone was minimal during the test because reactions maintained low aqueous-phase TCE concentrations. PMID:21591672

  1. 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.

  2. 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.

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

    PubMed

    Busch, Jan; Meiner, 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?m) are investigated in column tests using columns of 40cm length, which were filled with porous media. A suspension was pumped through the column under different physicochemical conditions (addition of a polyanionic stabilizer and changes in pH and ionic strength). Highest observed breakthrough was 62% of the injected concentration in glass beads with addition of stabilizer. Addition of mono- and bivalent salt, e.g. more than 0.5mM/L CaCl2, can decrease mobility and changes in pH to values below six can inhibit mobility at all. Measurements of colloid sizes and zeta potentials show changes in the mean particle size by a factor of ten and an increase of zeta potential from -62mV to -80mV during the transport experiment. However, results suggest potential applicability of c-nZVI under field conditions. PMID:24914524

  4. 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.

  5. Nitrate Removal by Acid-Washed Sulfur Modified Iron (SMI) and Zero Valent Iron (ZVI)

    NASA Astrophysics Data System (ADS)

    Han, K.; Ko, J.; Hong, U.; Lim, J.; Park, S.; Kwon, S.; Kim, Y.

    2010-12-01

    Sulfur Modified Iron (SMI) and Zero Valent Iron (ZVI) have been extensively studied for its ability to reduce different contaminants, including nitrate in groundwater. Although nitrate reduction with ZVI was reported as early as 1964, research projects using the materials as an alternative for nitrate removal have emerged only recently. Therefore, further investigations are still need to maximize the efficiency of nitrate removal using SMI and ZVI. In current work, we determined the mixing ratio, effects of acidification of SMI and ZVI, and need of pH controlling to obtain the highest nitrate removal rate, increasing amount of less expensive compound, ZVI, than SMI. In the results, nitrate removal by only ZVI or SMI was 32.53% and 0.69%, respectively. Although SMI:ZVI(1:4; g/g) was the best mixing ratio for the highest nitrate removal rate, it did not improve the removal rate compared to it when we used only ZVI or SMI. However, the acidified SMI and ZVI (1:4; g/g) with 0.5 N-HCl for 8 hr increased nitrate removal from 32% to 87%. Through the test, we found that using SMI and ZVI (1:4; g/g) acidified is an appropriate method to remediate nitrate-contaminated groundwater with the highest efficiency, increasing ratio of cheaper compound ZVI. Although SMI and ZVI showed the higher nitrate removal rate in low pH in other works, in case of using acidified SMI and ZVI, pH controlling did not affect the nitrate removal rate.

  6. Modelling the long-term performance of zero-valent iron using a spatio-temporal approach for iron aging

    NASA Astrophysics Data System (ADS)

    Kouznetsova, Irina; Bayer, Peter; Ebert, Markus; Finkel, Michael

    2007-02-01

    Zero-valent iron (ZVI) permeable reactive barriers (PRBs) have become popular for the degradation of chlorinated ethenes (CEs) in groundwater. However, a knowledge gap exists pertaining to the longevity of ZVI. The present investigation addresses this situation by suggesting a numerical simulation model that is intended to be used in conjunction with field or column tests in order to describe long-term ZVI performance at individual sites. As ZVI aging processes are not yet completely understood and are still subject to research, we propose a phenomenological modelling technique instead of a common process-based approach. We describe ZVI aging by parameters that characterise the extent and rate of ZVI reactivity change depending on the propagation of the precipitation front through ZVI. We approximate degradation of CEs by pseudo-first order kinetics accounting for the formation of partially dechlorinated products, and describe ZVI reactivity change by scaling the degradation rate constants. Three independent modelling studies were carried out to test the suitability of the conceptual and numerical model to describe the observations of accelerated column tests. All three tests indicated that ZVI reactivity declined with an increasing number of exchanged pore volumes. Measured and modelled concentrations showed good agreement, thereby proving that resolving spatial as well as temporal changes in ZVI reactivity is reasonable.

  7. 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 experiments were performed to determine the impact of agar agar on the reactivity of milled ZVI and investigate the apparent corrosion rate of particles by quantifying the hydrogen gas generated by anaerobic corrosion of milled ZVI. The results indicate that agar agar had a positive impact on the milled ZVI stability and mobility, however adverse impact on the reactivity towards trichloroethene (TCE) was observed compared to the non-stabilized material. On the other hand, this study shows that the apparent corrosion rate of non-stabilized and agar agar stabilized milled ZVI particles is in the same order of magnitude. These data indicate that the dechlorination pathway of TCE by agar agar stabilized milled ZVI particles is possibly impacted by blocking of the reactive sites and not hydrogen revealed during particles corrosion. Finally, calculated longevity of the particles based on the apparent corrosion rate is significantly prolonged compared to the longevity of the nZVI particles reported in previous studies. This research receives funding from the European Union's Seventh Framework Programme FP7/2007-2013 under grant agreement n°309517.

  8. 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 XANES/EXAFS, which could result in reduced mobility and toxicity of arsenic. Fourth, magnetite is a good adsorbent for both As(V) and As(III). As(V) was not reduced by stoichiometric magnetite even under a strictly anoxic condition. Addition of dissolved Fe(II) to magnetite did not reduce As(V) either. Under oxic conditions, the homogeneous oxidation of As(III) by dissolved oxygen was negligible. As(III) was rapidly oxidized in the presence of magnetite. The extent of the oxidation was promoted with addition of As(V). The effect is more significant at low As(III) concentrations. The effect could be important at field sites where total arsenic concentrations are low. This research is contributes to the understanding of the behavior of arsenic in sulfidic natural systems and in sites treated with GAC, ZVI-based permeable reactive barriers or injected with nano-ZVI particles. The optimum conditions and kinetic data for arsenic removal are applicable in field situations and engineered systems.

  9. Microbial reduction of nitrate in the presence of nanoscale zero-valent iron.

    PubMed

    Shin, Kyung-Hee; Cha, Daniel K

    2008-05-01

    Microbial reduction of nitrate in the presence of nanoscale zero-valent iron (NZVI) was evaluated to assess the feasibility of employing NZVI in the biological nitrate treatment. Nitrate was completely reduced within 3d in a nanoscale Fe(0)-cell reactor, while only 50% of the nitrate was abiotically reduced over 7d at 25 degrees C. The removal rate of nitrate in the integrated NZVI-cell system was unaffected by the presence of high amounts of sulfate. Efficient removal of nitrate by Fe(II)-supported anaerobic culture in 14 d indicated that Fe(II), which is produced during anaerobic iron corrosion in the Fe(0)-cell system, might act as an electron donor for nitrate. Unlike abiotic reduction, microbial reduction of nitrate was not significantly affected by low temperature conditions. This study demonstrated the potential applicability of employing NZVI iron as a source of electrons for biological nitrate reduction. Use of NZVI for microbial nitrate reduction can obviate the disadvantages associated with traditional biological denitrification, that relies on the use of organic substrates or explosive hydrogen gas, and maintain the advantages offered by nano-particle technology such as higher surface reactivity and functionality in suspensions. PMID:18331753

  10. 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

  11. [Removal of arsenate from drinking water by activated carbon supported nano zero-valent iron].

    PubMed

    Zhu, Hui-jie; Jia, Yong-feng; Yao, Shu-hu; Wu, Xing; Wang, Shu-ying

    2009-12-01

    A new adsorbent, activated carbon impregnated with nano zero-valent iron was prepared, which size of the needle-shaped iron particles in the pores of carbon was (30-500) nm x (1000-3000) nm and approximately 8.2% of iron was loaded onto it. The arsenate removal percentage was 99.5% by 1.5 g/L NZVI/AC in the 2 mg/L arsenic solution at pH 6.5 and (25 +/- 2) degrees C. The adsorption capacity was about 15.4 mg/g when equilibrium concentration was 1.0 mg/L. Kinetics revealed that uptake of arsenate ion by NZVI/AC was 91.4% in the first 12 h and equilibrium time was about 72 h. The intraparticle diffusion model was applied to study the mechanics of arsenate in the activated carbon. The presence of phosphate and silicate could significantly decrease arsenate removal while the effects of the other anions and cations on the arsenic removal were neglectable. NZVI/AC can be effectively regenerated when elution is done with 0.1 mol/L NaOH solution. Our results suggest that NZVI/AC is a suitable candidate for drinking water treatment due to its high reactivity. PMID:20187387

  12. 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

  13. 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

  14. 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.

  15. Polyelectrolyte multilayer film-assisted formation of zero-valent iron nanoparticles onto polymer nanofibrous mats

    NASA Astrophysics Data System (ADS)

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

    2009-09-01

    A facile approach that combines the electrospinning technique and layer-by-layer (LbL) assembly method has been developed to synthesize and immobilize zero-valent iron nanoparticles (ZVI NPs) onto the surface of nanofibers for potential environmental applications. In this approach, negatively charged cellulose acetate (CA) nanofibers fabricated by electrospinning CA solution were modified with bilayers composed of positively charged poly(diallyl-dimethyl-ammoniumchloride) (PDADMAC) and negatively charged poly(acrylic acid) (PAA) through electrostatic LbL assembly approach to form composite nanofibrous mats. The composite nanofibrous mats were immersed into the ferrous iron solution to allow Fe(II) ions to complex with the free carboxyl groups of PAA, and then ZVI NPs were immobilized onto the composite nanofibrous mats instantly by reducing the ferrous cations. Combined scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), and thermogravimetry analysis demonstrated that the ZVI NPs are successfully synthesized and uniformly distributed into the polyelectrolyte (PE) multilayer films assembled onto the CA nanofibers. The present approach to synthesis ZVI NPs opens a new avenue to fabricating various materials with high surface area for environmental, catalytic, and sensing applications.

  16. Bioinhibitory effect of hydrogenotrophic bacteria on nitrate reduction by nanoscale zero-valent iron.

    PubMed

    An, Yi; Dong, Qi; Zhang, Keqiang

    2014-05-01

    Hydrogenotrophic bacteria (HTB) were introduced into a nitrate removal system, which used nanoscale zero-valent iron (nZVI) as reductant, to investigate its bioinhibitory effect. Based on the results, it was noted that addition of HTB culture (10-50 mL) led to 58.9-91.4% decrease in the first observed rate constant (kobs1), which represented the nitrate removal rate by nZVI, and a reduction in the generated poisonous by-products from 94.9% to 38.5%. In other words, HTB had a significant inhibitory effect on nitrate reduction by nZVI. However, the pathway of this bioinhibition only prevented the occurrence of chemical reduction, but not competition for nitrate. Furthermore, FeOOH coating was observed on the surface of nZVI, instead of Fe3O4 or Fe2O3, which could prevent electron transmission from nZVI to nitrate. Considering that FeOOH was the product of iron corrosion, the result indicated that HTB could inhibit chemical reduction by enhancing the reaction between nZVI and water. PMID:24331034

  17. 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

  18. 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

  19. 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

  20. ARSENATE AND ARSENITE REMOVAL BY ZERO-VALENT IRON: EFFECTS OF PHOSPHATE, SILICATE, CARBONATE, BORATE, SULFATE, CHROMATE, MOLYBDATE, AND NITRATE, RELATIVE TO CHLORIDE: JOURNAL ARTICLE

    EPA Science Inventory

    NRMRL-ADA-01667 Su, C., and Puls*, R.W. Arsenate and Arsenite Removal by Zero-Valent Iron: Effects of Phosphate, Silicate, Carbonate, Borate, Sulfate, Chromate, Molybdate, and Nitrate, Relative to C...

  1. 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 ...

  2. 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.

  3. 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.

  4. 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.

  5. 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

  6. 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

  7. 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

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

    PubMed

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

    2014-01-01

    Zero-valent iron (ZVI) and green rusts can be used as reductants to convert chromium from soluble, highly toxic Cr(VI) to insoluble Cr(III). This study compared the reduction rates of Cr(VI) by ZVI and two carbonate green rust phases in alkaline/hyperalkaline solutions. Batch experiments were carried out with synthetic chromate solutions at pH 7.7-12.3 and a chromite ore processing residue (COPR) leachate (pH approximately 12.2). Green rust removes chromate from high pH solutions (pH 10-12.5) very rapidly (<400 s). Chromate reduction rates for both green rust phases were consistently higher than for ZVI throughout the pH range studied; the surface area normalized rate constants were two orders of magnitude higher in the COPR leachate solution at pH 12.2. The performances of both green rusts were unaffected by changes in pH. In contrast, ZVI exhibited a marked decline in reduction rate with increasing pH to become almost ineffective above pH12. PMID:24600891

  9. 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

  10. Mechanisms for removal of p-nitrophenol from aqueous solution using zero-valent iron.

    PubMed

    Nakatsuji, Yusuke; Salehi, Zeinab; Kawase, Yoshinori

    2015-04-01

    Batch experiments were conducted to examine mechanisms for removal of p-nitrophenol (PNP) from aqueous solution using zero-valent iron (ZVI). Removal of PNP using ZVI was mainly attributed to three mechanisms: degradation, precipitation and adsorption. A complete removal of 30mgL(-1) PNP with ZVI dosage of 1000mgL(-1) achieved within 30min at pH 3. The PNP removal rate in the acidic solutions was significantly suppressed at higher pH. The modified Langmuir-Hinshelwood kinetic model could successfully describe the PNP removal process using ZVI at different pH conditions. Total organic carbon (TOC) removal efficiencies were found to be almost independent of pH. While the TOC removal at lower pH was profoundly affected by the reductive and/or oxidative degradation, the adsorption was favorable at higher pH. The effect of dissolved oxygen on PNP removal was investigated at pH 3 where a maximum contribution of oxidative degradation could be expected. The PNP removal in the anoxic system purged with nitrogen gas was quick as well as that in the system being open to the air. However, the TOC removal under the anoxic condition was negligible as compared with that in the oxic system. The profiles of the intermediates formed during the PNP degradation indicated that the reductive degradation was predominant in the initial phase of the removal and subsequently the oxidative degradation occurred. PMID:25662484

  11. 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)

  12. 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

  13. 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

  14. Characteristics of two types of stabilized nano zero-valent iron and transport in porous media.

    PubMed

    Lin, Yu-Hao; Tseng, Hui-Hsin; Wey, Ming-Yen; Lin, Min-Der

    2010-04-15

    Nano-scale zero-valent iron (NZVI) has been shown to be suitable for remediating contaminated aquifers. However, they usually aggregate rapidly and result in a very limited migration distance that inhibits their usefulness. This study employed poly acrylic acid (PAA) and carboxymethyl cellulose (CMC) to synthesize two types of stabilized styles of NZVI with finer sizes (namely PNZVI and CNZVI). The mobility of stabilized NZVI was also demonstrated on the basis of transport in porous media. The results show that the PNZVI has a uniform particle size of 12 nm. However, tens of CNZVI particles with diameters of 1-3 nm were packed into secondary particles. Both the PNZVI and the CNZVI exhibited amorphous structures, and the stabilizer was bound to particle surfaces in the form of bidentate bridging via the carboxylic group, which could provide both electrostatic and steric repulsion to prevent particle aggregation. This study also proposes presumed stabilized configurations of PNZVI and CNZVI to reasonably illustrate their different dispersed suspension types. On the basis of the breakthrough curves and mass recovery, this study observed that the mobility of PNZVI in classic Ca(2+) concentration of groundwater was superior to CNZVI. Nonetheless, the mobility of CNZVI would be decreased less significantly than PNZVI when encountering high Ca(2+) concentrations (40 mM). Presumably, increasing the pore flow velocity would enhance the mobility of stabilized NZVI. Overall, the results of this study indicate that PNZVI has the potential to become an effective reactive material for in situ groundwater remediation. PMID:20163828

  15. Arsenite removal from waters by zero valent iron: batch and column tests.

    PubMed

    Biterna, M; Antonoglou, L; Lazou, E; Voutsa, D

    2010-01-01

    This study investigates the efficiency of zero valent iron (ZVI) to remove arsenite from water. Batch experiments were carried out to study the removal rates of arsenite under different pH values and in the presence of low and high concentrations of various ions (chloride, carbonate, nitrate, phosphate, sulfate and borate), manganese and dissolved organic matter. Most of these parameters affect negatively the removal of arsenite. Particularly, borate and organic matter at high concentrations significantly inhibited the efficiency of ZVI. Column tests were carried out to investigate the removal of arsenic under dynamic conditions and breakthrough curves were found for arsenate, arsenite and a mixture of both. ZVI treatment was also applied to natural groundwaters with elevated arsenic concentrations under the geochemical conditions usually found in Greece. The method was efficient for groundwater containing As(V). However, in anoxic-reducing groundwaters with prevalence of As(III), treated water did not fulfill the guideline of 10 microg L(-1) for drinking water. Chlorination enhanced the ZVI efficiency producing concentrations below the proposed limit. PMID:19879627

  16. 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

  17. 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

  18. 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.

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

    PubMed

    Alvarado, Jorge S; Rose, Candace; Lafreniere, Lorraine

    2010-08-01

    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. PMID:20596593

  1. Effects of nano zero-valent iron on Klebsiella oxytoca and stress response.

    PubMed

    Sacc, Maria Ludovica; Fajardo, Carmen; Nande, Mar; Martn, Margarita

    2013-11-01

    Nano zero-valent iron (NZVI) is a new option for contaminated soil and groundwater treatment, despite little is known on their impact on environmental microorganisms. Klebsiella oxytoca K5 strain, isolated from the NZVI-treated soil, was used to investigate the bacterial, phenotypical and molecular response to commercial NZVI exposure. Cytotoxicity assays at three NZVI concentrations (1, 5 and 10mgmL(-1)) suggested a negligible bacteriostatic effect and the lack of bactericidal effect. Structural changes were analysed by electronic microscopy. Scanning electron microscopy revealed the presence of NZVI around some bacterial cells, but no apparent morphological changes were seen. NZVI attachment to the cell surface was confirmed by transmission electron microscopy, although most of them were not affected. A proteomic approach (two-dimensional electrophoresis, matrix-assisted laser desorption ionization time-of-flight mass spectrometry) was used to investigate NZVI impact. For the first time to our knowledge, results revealed that exposure of a soil bacterium to NZVI resulted in the overproduction of tryptophanase, associated with oxidative stress response. K5 may set up an adaptative stress response involving indole as a signal molecule to inform the bacterial population about environmental changes. These findings would improve knowledge on the molecular mechanisms underlying bacterial response to NZVI exposure. PMID:23893265

  2. The impact of zero-valent iron nanoparticles upon soil microbial communities is context dependent.

    PubMed

    Pawlett, Mark; Ritz, Karl; Dorey, Robert A; Rocks, Sophie; Ramsden, Jeremy; Harris, Jim A

    2013-02-01

    Nanosized zero-valent iron (nZVI) is an effective land remediation tool, but there remains little information regarding its impact upon and interactions with the soil microbial community. nZVI stabilised with sodium carboxymethyl cellulose was applied to soils of three contrasting textures and organic matter contents to determine impacts on soil microbial biomass, phenotypic (phospholipid fatty acid (PLFA)), and functional (multiple substrate-induced respiration (MSIR)) profiles. The nZVI significantly reduced microbial biomass by 29 % but only where soil was amended with 5 % straw. Effects of nZVI on MSIR profiles were only evident in the clay soils and were independent of organic matter content. PLFA profiling indicated that the soil microbial community structure in sandy soils were apparently the most, and clay soils the least, vulnerable to nZVI suggesting a protective effect imparted by clays. Evidence of nZVI bactericidal effects on Gram-negative bacteria and a potential reduction of arbuscular mycorrhizal fungi are presented. Data imply that the impact of nZVI on soil microbial communities is dependent on organic matter content and soil mineral type. Thereby, evaluations of nZVI toxicity on soil microbial communities should consider context. The reduction of AM fungi following nZVI application may have implications for land remediation. PMID:23007947

  3. Oxidation of polyvinyl alcohol by persulfate activated with heat, Fe2+, and zero-valent iron.

    PubMed

    Oh, Seok-Young; Kim, Hyeong-Woo; Park, Jun-Mo; Park, Hung-Suck; Yoon, Chohee

    2009-08-30

    The oxidation of polyvinyl alcohol (PVA) by persulfate (S(2)O(8)(2-)) activated with heat, Fe(2+), and zero-valent iron (Fe(0)) was investigated via batch experiments. It was hypothesized that elevated temperature and the addition of Fe(2+) or Fe(0) into a persulfate-water system could enhance the oxidation of PVA by activated persulfate. Increasing the temperature from 20 to 60 degrees C or 80 degrees C accelerated the oxidation rate of PVA, which achieved complete oxidation in 30 and 10 min, respectively. At 20 degrees C, the addition of Fe(2+) or Fe(0) to the persulfate-water system significantly enhanced the oxidation of PVA. The optimal persulfate-to-Fe(2+) or Fe(0) molar ratio was found to be 1:1. Complete oxidation of PVA was obtained by Fe(0)-activated persulfate in 2h. Synergistic activation of persulfate by heat and Fe(2+) or Fe(0) was also shown to enhance the oxidation of PVA in the persulfate-water system. By using GC-MS analysis, an oxidation product of PVA was identified as vinyl acetic acid (C(4)H(6)O(2)), which is readily biodegradable. Our results suggest that the oxidative treatment of PVA by activated persulfate is a viable option for the pretreatment of PVA-laden wastewater to enhance its biodegradability. PMID:19285795

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

    PubMed

    HonetschlÄgerová, Lenka; Janouškovcová, Petra; Kubal, Martin

    2016-06-01

    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

  5. 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

  6. 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.

  7. 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.

  8. Modelling of geochemical and isotopic changes in a column experiment for degradation of TCE by zero-valent iron

    NASA Astrophysics Data System (ADS)

    Prommer, Henning; Aziz, Lidia H.; Bolao, Nerea; Taubald, Heinrich; Schth, Christoph

    2008-04-01

    Zero-valent iron (ZVI) permeable-reactive barriers have become an increasingly used remediation option for the in situ removal of various organic and inorganic chemicals from contaminated groundwater. In the present study a process-based numerical model for the transport and reactions of chlorinated hydrocarbon in the presence of ZVI has been developed and applied to analyse a comprehensive data set from laboratory-scale flow-through experiments. The model formulation includes a reaction network for the individual sequential and/or parallel transformation of chlorinated hydrocarbons by ZVI, for the resulting geochemical changes such as mineral precipitation, and for the carbon isotope fractionation that occurs during each of the transformation reactions of the organic compounds. The isotopic fractionation was modelled by formulating separate reaction networks for lighter ( 12C) and heavier ( 13C) isotopes. The simulation of a column experiment involving the parallel degradation of TCE by hydrogenolysis and ?-elimination can conclusively reproduce the observed concentration profiles of all collected organic and inorganic data as well as the observed carbon isotope ratios of TCE and its daughter products.

  9. 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 30C. 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

  10. 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

  11. Synthesis of Highly Reactive Subnano-sized Zero-valent Iron using Smectite Clay Templates

    PubMed Central

    Gu, Cheng; Jia, Hanzhang; Li, Hui; Teppen, Brian J.; Boyd, Stephen A.

    2010-01-01

    A novel method was developed for synthesizing subnano-sized zero-valent iron (ZVI) using smectite clay layers as templates. Exchangeable Fe(III) cations compensating the structural negative charges of smectites were reduced with NaBH4, resulting in the formation of ZVI. The unique structure of smectite clay, in which isolated exchangeable Fe(III) cations reside near the sites of structural negative charges, inhibited the agglomeration of ZVI resulting in the formation of discrete regions of subnanoscale ZVI particles in the smectite interlayer regions. X-ray diffraction revealed an interlayer spacing of ~ 5 . The non-structural iron content of this clay yields a calculated ratio of two atoms of ZVI per three cation exchange sites, in full agreement with the XRD results since the diameter of elemental Fe is 2.5 . The clay-templated ZVI showed superior reactivity and efficiency compared to other previously reported forms of ZVI as indicated by the reduction of nitrobenzene; structural Fe within the aluminosilicate layers was nonreactive. At a 1:3 molar ratio of nitrobenzene:non-structural Fe, a reaction efficiency of 83% was achieved, and over 80% of the nitrobenzene was reduced within one minute. These results confirm that non-structural Fe from Fe(III)-smectite was reduced predominantly to ZVI which was responsible for the reduction of nitrobenzene to aniline. This new form of subnano-scale ZVI may find utility in the development of remediation technologies for persistent environmental contaminants, e.g. as components of constructed reactive domains such as reactive caps for contaminated sediments. PMID:20446730

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

    NASA Astrophysics Data System (ADS)

    Busch, Jan; Oswald, Sascha

    2013-04-01

    The use of nano zero-valent iron (nZVI) for environmental remediation is an emerging technology for in situ remediation of contaminated groundwater. Due to its high surface area and high reactivity nZVI is able to dechlorinate organic contaminants and render them to less harmful substances. Carbo-Iron is a newly developed material consisting of activated carbon particles (d50 = 0.6 - 2.4 µm) that are doted with nZVI particles. These particles combine the sorption capacity of activated carbon and the reactivity of nZVI. Additionally the main limitation for nZVI delivery, a limited mobility due to fast aggregation and sedimentation of nZVI in dispersions and soils, might be solved. According to transport theory, particles with a diameter of approximately 1 µm are more mobile than unsupported nZVI particles in sandy aquifer systems. Results from column tests and a two dimensional laboratory aquifer test system are presented: Column tests using columns of 40 cm length were filled with sand. A particle suspension was pumped against gravity through the system. Results show, addition of a polyanionic stabilizer such as Carboxymethylcellulouse (CMC) is required to enhancing mobility. Ionic strength and pH concentrations in an environmental relevant range do not interfere significantly with transport, but particle size was found to be crucial. Another experiment was performed in a two dimensional aquifer test system. The test system contains a sand filled container with a inner size of 40 x 5 x 110 cm and seven ports on each side. A constant flow of water was applied from the left to the right side through all ports and the middle port was fed with a Carbo-Iron suspension. Results show a transport through the laboratory aquifer within few exchanged pore volumes, and breakthrough of Carbo-Iron at the outlet. Deposits of immobile Carbo-Iron were found to be decreasing with distance from the injection port. No gravity effects were observed. Results suggest high mobility of carbon supported nZVI under environmental relevant conditions. Carbo-Iron might be helpful to deliver nZVI into contaminated aquifers. There 1D and 2D results support the design of a field test and application of Carbo-Iron for nZVI delivery.

  13. 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.

  14. Weak magnetic field accelerates chromate removal by zero-valent iron.

    PubMed

    Feng, Pian; Guan, Xiaohong; Sun, Yuankui; Choi, Wonyong; Qin, Hejie; Wang, Jianmin; Qiao, Junlian; Li, Lina

    2015-05-01

    Weak magnetic field (WMF) was employed to improve the removal of Cr(VI) by zero-valent iron (ZVI) for the first time. The removal rate of Cr(VI) was elevated by a factor of 1.12-5.89 due to the application of a WMF, and the WMF-induced improvement was more remarkable at higher Cr(VI) concentration and higher pH. Fe2+ was not detected until Cr(VI) was exhausted, and there was a positive correlation between the WMF-induced promotion factor of Cr(VI) removal rate and that of Fe2+ release rate in the absence of Cr(VI) at pH4.0-5.5. These phenomena imply that ZVI corrosion with Fe2+ release was the limiting step in the process of Cr(VI) removal. The superimposed WMF had negligible influence on the apparent activation energy of Cr(VI) removal by ZVI, indicating that WMF accelerated Cr(VI) removal by ZVI but did not change the mechanism. The passive layer formed with WMF was much more porous than without WMF, thereby facilitating mass transport. Therefore, WMF could accelerate ZVI corrosion and alleviate the detrimental effects of the passive layer, resulting in more rapid removal of Cr(VI) by ZVI. Exploiting the magnetic memory of ZVI, a two-stage process consisting of a small reactor with WMF for ZVI magnetization and a large reactor for removing contaminants by magnetized ZVI can be employed as a new method of ZVI-mediated remediation. PMID:25968271

  15. 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.

  16. Hydrogen production from the dissolution of nano zero valent iron and its effect on anaerobic digestion.

    PubMed

    Huang, Yu-Xi; Guo, Jialiang; Zhang, Chunyang; Hu, Zhiqiang

    2016-01-01

    Nano zero valent iron (NZVI) has shown inhibition on methanogenesis in anaerobic digestion due to its reductive decomposition of cell membrane. The inhibition was accompanied by the accumulation of hydrogen gas due to rapid NZVI dissolution. It is not clear whether and how rapid hydrogen release from NZVI dissolution directly affects anaerobic digestion. In this study, the hydrogen release kinetics from NZVI (average size=5511nm) dissolution in deionized water under anaerobic conditions was first evaluated. The first-order NZVI dissolution rate constant was 2.620.26h(-1) with its half-life of 0.260.03h. Two sets of anaerobic digestion experiments (i.e., in the presence of glucose or without any substrate but at different anaerobic sludge concentrations) were performed to study the impact of H2 release from rapid NZVI dissolution, in which H2 was generated in a separate water bottle containing NZVI (i.e., ex situ H2 or externally supplied from NZVI dissolution) before hydrogen gas was introduced to anaerobic digestion. The results showed that the H2 partial pressure in the headspace of the digestion bottle reached as high as 0.27atm due to rapid NZVI dissolution, resulting in temporary inhibition of methane production. Nevertheless, the 5-d cumulative methane volume in the group with ex situ H2 production due to NZVI dissolution was actually higher than that of control, suggesting NZVI inhibition on methanogenesis is solely due to the reductive decomposition of cell membrane after direct contact with NZVI. PMID:26521217

  17. Fine structure characterization of zero-valent iron nanoparticles for decontamination of nitrites and nitrates in wastewater and groundwater

    NASA Astrophysics Data System (ADS)

    Lin, Kuen-Song; Chang, Ni-Bin; Chuang, Tien-Deng

    2008-04-01

    The main objectives of the present study were to investigate the chemical reduction of nitrate or nitrite species by zero-valent iron nanoparticle (ZVIN) in aqueous solution and related reaction kinetics or mechanisms using fine structure characterization. This work also exemplifies the utilization of field emission-scanning electron microscope (FE-SEM), transmission electron microscopy (TEM), and x-ray diffraction (XRD) to reveal the speciation and possible reaction pathway in a very complex adsorption and redox reaction process. Experimentally, ZVIN of this study was prepared by sodium borohydride reduction method at room temperature and ambient pressure. The morphology of as-synthesized ZVIN shows that the nearly ball and ultrafine particles ranged of 20-50 nm were observed with FE-SEM or TEM analysis. The kinetic model of nitrites or nitrates reductive reaction by ZVIN is proposed as a pseudo first-order kinetic equation. The nitrite and nitrate removal efficiencies using ZVIN were found 65-83% and 51-68%, respectively, based on three different initial concentrations. Based on the XRD pattern analyses, it is found that the quantitative relationship between nitrite and Fe(III) or Fe(II) is similar to the one between nitrate and Fe(III) in the ZVIN study. The possible reason is due to the faster nitrite reduction by ZVIN. In fact, the occurrence of the relative faster nitrite reductive reaction suggested that the passivation of the ZVIN have a significant contribution to iron corrosion. The extended x-ray absorption fine structure (EXAFS) or x-ray absorption near edge structure (XANES) spectra show that the nitrites or nitrates reduce to N2 or NH3 while oxidizing the ZVIN to Fe2O3 or Fe3O4 electrochemically. It is also very clear that decontamination of nitrate or nitrite species in groundwater via the in-situ remediation with a ZVIN permeable reactive barrier would be environmentally attractive.

  18. Enhanced Perchloroethylene Reduction Using Surfactant-Modified Zeolite/Zero-Valent Iron Pellets

    NASA Astrophysics Data System (ADS)

    Zhang, P.; Tao, X.; Bowman, R. S.

    2001-12-01

    We determined the effect of surfactant modification on perchloroethylene (PCE) reduction by zeolite/zero-valent iron (ZVI) pellets. We packed the pellets into four columns (30-cm long, 4.8-cm diameter) and modified two of the columns by sorbing the cationic surfactant hexadecyltrimethylammonium chloride (HDTMA-Cl) onto the pellets. We then continuously injected 11.0 ? M PCE into the columns and monitored the effluent concentrations of PCE, trichloroethylene (TCE), cis-, trans-, and 1,1-dichloroethylene (DCE), and vinyl chloride. The effluent PCE concentrations for the surfactant-modified columns were significantly lower than those for the unmodified columns (i.e., by factors of 6, 4, and 3 at pore water velocities of 0.5, 1.0, and 2.0 m/day, respectively). PCE reduction rate constants were three times higher for the modified columns relative to the unmodified columns at the three velocities. For a given column, the PCE reduction rate constant did not decrease as the pore water velocity increased from 0.5 m/day to 2.0 m/day. TCE was observed in the effluent of the modified and unmodified columns, with the concentrations for the modified columns (0.2, 0.4, and 0.7 ? M at 0.5, 1.0, and 2.0 m/day, respectively) roughly 10 times higher than those for the unmodified columns. No cis-DCE was detected in the effluent of the unmodified columns, whereas noticeable amounts (0.01-0.03 ? M) of cis-DCE were observed in the effluent of the modified columns. No trans-DCE, 1,1-DCE, or vinyl chloride was detected in the effluents of the modified or unmodified columns. Our results clearly demonstrate that the modification of zeolite/ZVI pellets with HDTMA significantly enhances PCE reduction. The enhanced PCE reduction may be due to an increased local PCE concentration in the vicinity of ZVI surface as a result of PCE sorption by the modified pellets. Our data also suggest that the PCE reduction mechanism for the modified pellets differs from that for the unmodified pellets, as seen by the much higher TCE and cis-DCE generation with the modified pellets.

  19. 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 (?-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 ?-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 ?-value is affected by the starting concentration of PCE (?-value of c1 < c2) as there is a higher ratio of PCE to ZVI.

  20. Effects of alcohols, anionic and nonionic surfactants on the reduction of PCE and TCE by zero-valent iron.

    PubMed

    Loraine, G A

    2001-04-01

    The effects of surfactants, sodium dodecyl sulfate (SDS) and Triton X-a00 (TX), and alcohols (methanol, ethanol, and propanol) on the dehalogenation of TCE and PCE by zero-valent iron were examined. Surface concentrations of PCE and TCE on the iron were dependent on aqueous surfactant concentrations. At concentrations above the CMC, sorbed halocarbon concentrations declined and concentrations associated with solution phase micelles increased. The anionic surfactant SDS ([SDS] < CMC) did not affect reduction rates, until the CMC was exceeded after which reactivity decreased, possibly due to sequestering of the TCE and PCE in mobile micelles. The nonionic TX showed a mixed effect on reactivity, increasing the PCE reduction rate, but not affecting TCE removal. Production of TCE from PCE increased in the presence of TX. Similar experiments showed that methanol, ethanol, and propanol inhibited reduction of TCE and PCE by metallic iron. Zero-valent iron may be useful in recycling soil washing effluents contaminated with TCE and PCE. PMID:11317892

  1. 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.

  2. 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

  3. Investigation into the potential toxicity of zero-valent iron nanoparticles to a trichloroethylene-degrading groundwater microbial community

    NASA Astrophysics Data System (ADS)

    Zabetakis, Kara M.

    The microbiological impact of zero-valent iron remediation of groundwater was investigated by exposing a trichloroethylene-degrading anaerobic microbial community to bare and coated iron nanoparticles. Changes in population numbers and metabolic activity were analyzed using qPCR and were compared to those of a blank, negative, and positive control to assess for microbial toxicity. Additionally, these results were compared to those of samples exposed to an equal concentration of iron filings in an attempt to discern the source of toxicity. Statistical analysis revealed that the three iron treatments were equally toxic to total Bacteria and Archaea populations, as compared with the controls. Therefore, toxicity appears to result either from the release of iron ions and the generation of reactive oxygen species, or from alteration of the redox system and the disruption of microbial metabolisms. There does not appear to be a unique nanoparticle-based toxicity.

  4. Batch-test study on the dechlorination of 1,1,1-trichloroethane in contaminated aquifer material by zero-valent iron

    NASA Astrophysics Data System (ADS)

    Lookman, Richard; Bastiaens, Leen; Borremans, Brigitte; Maesen, Miranda; Gemoets, Johan; Diels, Ludo

    2004-10-01

    Chlorinated aliphatic hydrocarbons are common groundwater contaminants. One possible remediation option is in-situ reductive dechlorination by zero-valent iron, either by direct injection or as reactive barriers. Chlorinated ethenes (tetrachloroethene: PCE; trichloroethene: TCE) have received extensive attention in this context. However, another common groundwater pollutant, 1,1,1-trichlorethane (TCA), has attracted much less attention. We studied TCA reduction by three types of granular zero-valent irons in a series of batch experiments using polluted groundwater, with and without added aquifer material. Two types of iron were able to reduce TCA completely with no daughter product concentration increases (1,1-dichloroethane: DCA; chloroethane: CA). One type of iron showed slower reduction, with intermediate rise of DCA and CA concentrations. When evaluating the formation of daughter products, the tests on the groundwater alone showed different results than the groundwater plus aquifer batches: DCA did not temporarily accumulate in the batches with added aquifer material, contrary to the batches without added aquifer material. 1,1-dichloroethene (DCE, also present in the groundwater as an abiotic degradation product of TCA) was also reduced slower in the batches without added aquifer material than in the batches with aquifer material. Redox potentials gradually decreased to low values in batches with aquifer material without iron, while the batches with groundwater alone maintained a constant higher redox potential. Either adsorption processes or microbiological activity in the samples could explain these phenomena. Polymerase Chain Reaction (PCR: a targeted gene probe technique) for chlorinated aliphatic compound (CAH)-degrading bacteria confirmed the presence of Dehalococcoides sp. (chloroethene-degraders) but was negative for Desulfobacterium autotrophicum (a known co-metabolic TCA degrader). DCA reduction was rate determining: first-order half-lives of 300-350 h were observed. TCA was fully removed within hours. CA is resistant to reduction by zero-valent iron but it is known to hydrolyze easily. Since CA did not accumulate in our batches, it may have disappeared by the latter mechanism or it may not have formed as a major daughter product.

  5. Transport of zero-valent iron nanoparticles in carbonate-rich porous aquifers

    NASA Astrophysics Data System (ADS)

    Laumann, S.; Micic, V.; Hofmann, T.

    2012-04-01

    Use of nanoscale zero-valent iron (nZVI) for in situ dechlorination of chlorinated solvents in groundwater is a promising remediation technology, due to a high dechlorination efficiency of nZVI and possible applications in e.g., great depth or under above-ground infrastructure. The success of the in situ nZVI dechlorination strongly depends on the particle delivery to the contaminants. Previous studies reported a limited transport of nZVI through porous media (cm- to dm-range) and this has been recognized as one of the major obstacles in a widespread utilization of this technology (TRATNYEK & JOHNSON, 2006). Factors that limit the transport are particle aggregation and deposition onto the aquifer solids. Both depend on particle properties (e.g., size, shape, iron content, surface coating, surface charge), on concentrations of suspensions, and on site-specific parameters, such as the groundwater chemistry and the properties and inhomogeneity of the aquifer material. Adsorbed anionic polyelectrolyte coatings provide electrostatic double layer repulsions between negatively charged nZVI particles (SALEH ET AL., 2007), hindering their aggregation and also deposition on the negatively charged quartz surfaces (usually prevailing in aquifers). However, it is shown that the presence of surface charge heterogeneities in the aquifer effects the particle transport (JOHNSON ET AL., 1996). Carbonates, iron oxides, and the edges of clay minerals, for instance, carry a positive surface charge at neutral pH (often encountered in groundwater). This leads to a favorable deposition of negatively charged nZVI particles onto carbonates, metal oxide impurities or clay edges, and finally to a decreased particle transport. Considering the high proportion of carbonates commonly encountered in Alpine porous aquifers, in this study we aimed to evaluate the transport of commercially available polyelectrolyte coated nZVI (polyacrylic acid coated-nZVI, NANOIRON s.r.o., CZ) in both quartz and carbonate-rich porous media and to quantify alteration in travel distances with the increasing proportion of carbonate sands. Transport studies using Nanofer 25S are carried out in 1 D columns filled with different proportions of quartz and carbonate sands at a pH typically encountered in groundwater. Column experiments demonstrated that the travel distance of coated-nZVI systematically decreases with increasing portion of carbonate sand. The transportability of Nanofer 25S was reduced by ~45% in pure carbonate sand, compared to that in pure quartz sand. These results demonstrated different attachment affinities of coated-nZVI for the investigated solids. Current experiments are carried out in order to provide a mechanistic understanding of the observed nanoparticle-solid matrix interactions. Furthermore, the effects of varying groundwater chemistry, size and shape of the packing material, as well as the presence of metal oxides and natural organic matter on the nZVI transport will be investigated. The project is funded by the Federal Ministry of Agriculture, Forestry, Environment and Water Management (BMLFUW). Management by Kommunalkredit Public Consulting GmbH. Literature TRATNYEK, P.G., JOHNSON, R.L., (2006): Nano Today 1, 44-48. SALEH, N. ET AL., (2007): Environmental Engineering Science24, 45-57. JOHNSON, P.R. ET AL., (1996): Environmental Science & Technology 30, 3284-3293.

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

    PubMed

    Sanchez, Irama; Stber, Frank; Fabregat, Azael; Font, Josep; Fortuny, Agust; 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 30C 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

  7. 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.

  8. 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.

  9. 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

  10. 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

  11. 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 metalwater interface and the effect that sorption has at the oxidewater interface on contaminant reduction kinetics. The results s...

  12. 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...

  13. 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.

  14. 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 ...

  15. 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...

  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. Carbonate minerals in porous media decrease mobility of polyacrylic acid modified zero-valent iron nanoparticles used for groundwater remediation.

    PubMed

    Laumann, Susanne; Mici?, Vesna; Lowry, Gregory V; Hofmann, Thilo

    2013-08-01

    The limited transport of nanoscale zero-valent iron (nZVI) in porous media is a major obstacle to its widespread application for in situ groundwater remediation. Previous studies on nZVI transport have mainly been carried out in quartz porous media. The effect of carbonate minerals, which often predominate in aquifers, has not been evaluated to date. This study assessed the influence of the carbonate minerals in porous media on the transport of polyacrylic acid modified nZVI (PAA-nZVI). Increasing the proportion of carbonate sand in the porous media resulted in less transport of PAA-nZVI. Predicted travel distances were reduced to a few centimeters in pure carbonate sand compared to approximately 1.6m in quartz sand. Transport modeling showed that the attachment efficiency and deposition rate coefficient increased linearly with increasing proportion of carbonate sand. PMID:23644276

  18. 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.

  19. Reductive dechlorination of activated carbon-adsorbed trichloroethylene by zero-valent iron: carbon as electron shuttle.

    PubMed

    Tang, Hao; Zhu, Dongqiang; Li, Tielong; Kong, Haonan; Chen, Wei

    2011-01-01

    Sequestration of organic contaminants in carbonaceous materials can significantly affect contaminant fate and transport. We investigated the reductive dechlorination of granular-activated carbon (GAC)-adsorbed trichloroethylene (TCE) by nanoscale zero-valent iron (nZVI) to understand the effect of sequestration on abiotic reactivity of organic contaminants. Significant reduction of TCE sequestered in GAC micropores was observed, even though direct contact with nZVI was unlikely. Reduction of sequestered TCE by reactive Fe(II) species or molecular hydrogen was ruled out as the reaction mechanisms. We propose that GAC served as the conductor for the transfer of electrons or atomic hydrogen from nZVI to the micropores, wherein adsorbed TCE molecules were reduced. An important implication for environmental remediation is that carbonaceous adsorbents not only function as a superb sink for organic contaminants but also allow them to be slowly degraded while being trapped. PMID:22031571

  20. Treatment of dissolved perchlorate, nitrate, and sulfate using zero-valent iron and organic carbon.

    PubMed

    Liu, YingYing; Ptacek, Carol J; Blowes, David W

    2014-05-01

    Waters containing ClO and dissolved NO, derived from detonated explosives and solid propellants, often also contain elevated concentrations of other dissolved constituents, including SO. Four column experiments, containing mixtures of silica sand, zero-valent Fe (ZVI) and organic C (OC) were conducted to evaluate the potential for simultaneous removal of NO, SO and ClO. Initially, the flow rate was maintained at 0.5 pore volumes (PV) d and then decreased to 0.1 PV d after 100 PV of flow. Nitrate concentrations decreased from 10.8 mg L (NO-N) to trace levels through NO reduction to NH using ZVI alone and through denitrification using OC. Observations from the mixture of ZVI and OC suggest a combination of NO reduction and denitrification. Up to 71% of input SO (24.5 3.5 mg L) was removed in the column containing OC, and >99.7% of the input ClO (857 63 ?g L) was removed by the OC- and (ZVI + OC)-containing columns as the flow rate was maintained at 0.1 PV d. Nitrate and ClO removal followed first-order and zero-order rates, respectively. Nitrate >2 mg L (NO-N) inhibited ClO removal in the OC-containing column but not in the (ZVI + OC)-containing column. Sulfate did not inhibit ClO degradation within any of the columns. PMID:25602813

  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 oxidant such as the ferryl ion [Fe(IV)] at neutral pH. This provides insight into the type of compounds that may be oxidized using the zero-valent iron and oxygen system. The addition of certain compounds such as oxalate and polyoxometalate (POM) may improve contaminant remediation efficiencies by enhancing oxidant yields. The introduction of 1 mM oxalate improved the formaldehyde yield by approximately 20% at neutral pH. Oxalate accelerates the Fenton reaction and limits the passivation of the ZVI surface by increasing iron solubility. The presence of excess POM greatly enhanced the yield of formaldehyde, with maximum yields of 60 and 35% with respect to ZVI added at pH 2 and 7, respectively. The mechanism of POM enhancement is a function of solution pH. At acidic pH, POM acts an electron shuttle by directly transferring electrons from ZVI to oxygen to increase the hydrogen peroxide production. At neutral pH, POM may act by forming soluble iron-complexes and preventing the build-up of an iron oxide layer on the ZVI surface.

  2. 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.

  3. Zero valent iron significantly enhances methane production from waste activated sludge by improving biochemical methane potential rather than hydrolysis rate.

    PubMed

    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

  4. 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

  5. Comparisons of the reactivity, reusability and stability of four different zero-valent iron-based nanoparticles.

    PubMed

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

    2014-08-01

    Our previous reports showed that nano zero-valent iron (nZVI), steel pickle liquor for the synthesis of nZVI (S-nZVI), nZVI immobilised in mesoporous silica microspheres (SiO2@FeOOH@Fe) and nano Ni/Fe bimetallic particles (Ni/Fe) have been proved to show good property for elimination of polybrominated diphenyl ethers (PBDEs). However, it is necessary to compare their reactivity, reusability and stability when applied to in situ remediation. In this study, the performances of different iron-based nanoparticles were compared through reusability, sedimentation and iron dissolution experiments. The SiO2@FeOOH@Fe and Ni/Fe nanoparticles were shown to have higher reusability and stability, as they could be reused more than seven times, and that the SiO2@FeOOH@Fe can effectively avoid leaching iron ions into the solution and causing secondary pollution in the reaction. This study may serve as a reference for PBDE remediation in the future. PMID:24582360

  6. 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

  7. 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

    2015-12-01

    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

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

    PubMed

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

    2015-01-01

    The reactivity of nanoscale zero valent iron (nZVI) toward targeted contaminants is affected by the initial nZVI composition and the iron oxides formed during the aging process in aquatic systems. In this paper, the aging effects of nZVI, prepared using a borohydride reduction method in static water over a period of 90 days (d), are investigated. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Raman spectroscopy are used to characterize the corrosion products of nZVI. Results show that both the structures and the compositions of the corrosion products change with the process of aging. The products of nZVI aged for 5 d in static water media are mainly magnetite (Fe3O4) and maghemite (?-Fe2O3), accompanied by lepidocrocite (?-FeOOH). For products aged 10 d, XRD data show the formation of ferrihydrite and lepidocrocite. When aged up to 90 d, the products are mainly ?-FeOOH mixed with small amounts of Fe3O4 and ?-Fe2O3. Transmission electronic microscopy (TEM) images show that the core-shell structure forms into a hollow spherical shape after 30 d of aging in aquatic media. The results indicate first that iron ions in the Fe(0) core diffuse outwardly toward the shell, and hollowed-out iron oxide shells emerge. Then, the iron oxide shell collapses and becomes a flaky, acicular-shaped structure. The type and the crystal phase of second iron oxide minerals are vastly different at various aging times. This study helps to explain the patterns of occurrence of specific iron oxides in different natural conditions. PMID:25317915

  9. 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 H? 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). H? evolution rates were determined for column experiments without and with hydrogen carbonate and/or calcium. On average 0.29 mmol H?/L per g Fe? evolved within the first 30 days in column experiments with spherical, commercial nZVI particles. The H? evolution developed almost independently of the water matrices applied. The application of nZVI flakes resulted in lower H? 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, Fe? 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

  10. 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

  11. 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

  12. 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

  13. 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

  14. 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

  15. Arsenic removal from geothermal waters with zero-valent iron--effect of temperature, phosphate and nitrate.

    PubMed

    Tyruvola, Konstantina; Nikolaidis, Nikolaus P; Veranis, Nikolaus; Kallithrakas-Kontos, Nikolaso; Koulouridakis, Pavlos E

    2006-07-01

    Field column studies and laboratory batch experiments were conducted in order to assess the performance of zero-valent iron in removing arsenic from geothermal waters in agricultural regions where phosphates and nitrates were present. A field pilot study demonstrated that iron filings could remove arsenic, phosphate and nitrate from water. In addition, batch studies were performed to evaluate the effect of temperature, phosphate and nitrate on As(III) and As(V) removal rates. All batch experiments were conducted at three temperatures (20, 30 and 40 degrees C). Pseudo-first-order reaction rate constants were calculated for As(III), As(V), phosphate, nitrate and ammonia for all temperatures. As(V) exhibited greater removal rates than As(III). The presence of phosphate and nitrate decreased the rates of arsenic removal. The temperature of the water played a dominant role on the kinetics of arsenic, phosphate and nitrate removal. Nitrate reduction resulted in the formation of nitrite and ammonia. In addition, the activation energy, Eact, and the constant temperature coefficient, theta were determined for each removal process. PMID:16769102

  16. 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

  17. Mobility enhancement of nanoscale zero-valent iron in carbonate porous media through co-injection of polyelectrolytes.

    PubMed

    Laumann, Susanne; Mici?, Vesna; Hofmann, Thilo

    2014-03-01

    The mobility of nanoscale zero-valent iron (nZVI), which is used for in situ groundwater remediation, is affected by chemical and physical heterogeneities within aquifers. Carbonate minerals in porous aquifers and the presence of divalent cations reduce nZVI mobility. This study assesses the potential for enhancing the mobility of polyacrylic acid coated nZVI (PAA-nZVI) in such aquifers through the co-injection of polyelectrolytes (natural organic matter, humic acid, carboxymethyl cellulose, and lignin sulfonate). When applied at the same concentration, all of the polyelectrolytes produced similar enhancement of PAA-nZVI mobility in carbonate porous media. This increase in mobility was a result of increased repulsion between PAA-nZVI and the carbonate matrix. Lignin sulfonate, an environmentally friendly and inexpensive agent, was identified as the most suitable polyelectrolyte for field applications. The greatest increase in PAA-nZVI mobility was achieved with co-injection of lignin sulfonate at concentrations ?50mgL(-1); at these concentrations the maximum PAA-nZVI travel distance in carbonate porous media was twice of that in the absence of lignin sulfonate. PMID:24361704

  18. 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

  19. 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.

  20. Treatment of phenol-containing wastewater by photoelectro-Fenton method using supported nanoscale zero-valent iron.

    PubMed

    Babuponnusami, Arjunan; Muthukumar, Karuppan

    2013-03-01

    This study presents the degradation of phenol by the photoelectro-Fenton method using nano zero-valent iron (nZVI) immobilized in polyvinyl alcohol-alginate beads. The effect of nZVI loading, H(2)O(2) concentration, pH, and initial phenol concentration on phenol degradation and chemical oxygen demand reduction was studied. The scanning electron microscope images of the nZVI beads were used to analyze their morphology, and their diameters were in the range of 500-600 ?m. The concentration of nZVI in the beads was varied from 0.1 to 0.6 g/L. Fe(2+) leakage of 1 and 3 % was observed with 0.5 and 0.6 g/L of nZVI, respectively, and the observed beads' fracture frequency was 2 %, which confirmed the stability of the beads. The optimum operating conditions that arrived for better degradation were 0.5 g/L of nZVI, pH 6.2, and 400 mg H(2)O(2)/L. The treatment of effluent by this method increased the biodegradability index of the effluent, and the degradation data were found to follow pseudo first-order kinetics. PMID:22711016

  1. Reductive transformation and detoxification mechanism of 2,4-dinitrochlorobenzene in combined zero valent iron and anaerobic-aerobic process.

    PubMed

    Shen, Jinyou; Zhou, Zongyuan; Ou, Changjin; Sun, Xiuyun; Li, Jiansheng; Han, Weiqing; Zhou, Lin; Wang, Lianjun

    2012-01-01

    A combined zero valent iron (ZVI) and anaerobic-aerobic process was adopted for the treatment of 2,4-dinitrochlorobenzene (DNCB)-containing wastewater. The transformation pathway, reduction of acute toxicity and enhancement of biodegradability were investigated. After pretreatment by ZVI, DNCB in wastewater could be completely converted into 2,4-diaminochlorobenzene (DACB). The ratio of BOD5/COD increased from 0.005 +/- 0.001 to 0.168 +/- 0.007, while EC(50, 48 hr) (V/V) increased from 0.65% to 5.20%, indicating the enhancement of biodegradability and reduction of acute toxicity with the pretreatment by ZVI. DACB was further dechlorinated to m-phenylenediamine during the anaerobic process using methanol as electron donor, with EC(50, 48 hr) increasing from 5.20% to 48.2%. After the subsequent anaerobic-aerobic process, m-phenylenediamine was degraded completely, with effluent COD of 67.5 +/- 10.8 mg/L. This effluent of the subsequent anaerobic-aerobic process was not toxic to zebrafish. The combined ZVI and anaerobic-aerobic process offers bright prospects for the treatment of chlorinated nitroaromatic compound-containing wastewater. PMID:23534221

  2. Influence of humic acid on the colloidal stability of surface-modified nano zero-valent iron.

    PubMed

    Dong, Haoran; Lo, Irene M C

    2013-01-01

    To enhance colloidal stability of nano zero-valent iron (NZVI) used for groundwater remediation, the surfaces of such NZVI can be modified via coating with organic stabilizers. These surface stabilizers can electrostatically, sterically, or electrosterically stabilize NZVI suspensions in water, but their efficacy is affected by the presence of humic acid (HA) in groundwater. In this study, the effect of HA on the colloidal stability of NZVI coated with three types of stabilizers (i.e., polyacrylic acid (PAA), Tween-20 and starch) was evaluated. Differing stability behaviors were observed for different surface-modified NZVIs (SM-NZVI) in the presence of HA. Fluorescence spectroscopic analysis probed the possible interactions at the SM-NZVI-HA interface, providing a better understanding of the effect of HA on SM-NZVI stability. The adsorption of HA on the surface of PAA-modified NZVI via complexation with NZVI (rather than the PAA stabilizer) enhanced the electrosteric repulsion effect, increasing the stability of the particles. However, for NZVI modified with Tween-20 or starch, HA could interact with the surface stabilizer and apparently play a "bridge" role among the particles, which might induce aggregation of the particles. Therefore, the stability behavior of NZVI modified with Tween-20 or starch might have resulted from the combined effect of "bridging" and "electrosteric" exerted by HA. PMID:23123051

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

    PubMed

    Kowalski, Krzysztof P; Sgaard, Erik G

    2014-12-01

    Arsenic in drinking water is concerning millions of people around the world, even though many solutions to the problem have come up in recent years. One of the promising solutions for removing arsenic from water is by implementation of a zero-valent iron (ZVI) in the drinking water production. The purpose of this work was to study a treatment of As pollution based on the ZVI, aeration and sand filtration that was monitored for period of 45 months. In applied configuration and conditions ZVI was not able to remove arsenic alone, but it worked as a source of ferrous ions that during its oxidation enabled to co-precipitate arsenic compounds in the sand filter. The results show that after a lag phase of about 6 months, it was possible to achieve water production with an As content from 20 ?g L(-1) to below 5 ?g L(-1). The treatment also enabled to remove phosphates that were present in groundwater and affected As uptake by hindering its co-precipitation with Fe compounds. Determination of colony forming units on As amended agar helped to find arsenic resistant bacteria at each stage of treatment and also in the sand filter backwash sludge. Bacterial communities found in groundwater, containing low concentration of As, were found to have high As resistance. The results also indicate that the lag phase might have been also needed to initiate Fe ions release by corrosion from elemental Fe by help of microbial activity. PMID:24996201

  4. 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 1.5h 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

  5. 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

  6. 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

  7. 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

  8. Enhanced colloidal stability of nanoscale zero valent iron particles in the presence of sodium silicate water glass.

    PubMed

    Honetschlgerov, Lenka; Janoukovcov, Petra; Kubal, Martin; Sofer, Zden?k

    2015-01-01

    A method for the stabilization of nanoscale zero valent iron (nZVI) particles using silica was developed. Stabilization can significantly improve the performance characteristics of currently available nZVI products containing agglomerated particles. In the first step of the method, the agglomerates were broken using a sonication. A subsequent stabilizing effect was brought about by the deposition of silica onto the surface of the nZVI particles. The method was tested on three commercially available nZVI suspensions which formed agglomerates with mean sizes ranging from 1000 to 5000?nm. The application of the method resulted in a significant reduction of the mean size of the agglomerates to the values from 100 to 200?nm. The stabilizing effect of silica was also evidenced using scanning electron microscopy, zeta potential measurements and sedimentation analysis. The introduction of typical groundwater ions did not significantly affect the colloidal stability of the treated nZVI suspensions. The results of this study indicate that the silica coating have the potential to protect nZVI against agglomeration. PMID:25323113

  9. Efficiency of nanoscale zero-valent iron on the enhanced low molecular weight organic acid removal Pb from contaminated soil.

    PubMed

    Wang, Guiyin; Zhang, Shirong; Xu, Xiaoxun; Li, Ting; Li, Yun; Deng, Ouping; Gong, Guoshu

    2014-12-01

    The Pb removal efficiencies from contaminated soils by low molecular weight organic acid (LMWOA) and nanoscale zero-valent iron (nZVI) were investigated through batch soil washing experiments. Results showed that significant promotion on Pb-removal with the mixed solutions of LMWOA and nZVI (p < 0.05). The Pb removal efficiencies reached 64% and 83% for mine and farmland soil by addition of 0.2 M citric acid and 2.0 g L?1 nZVI, respectively. They decreased with increasing pH from 3 to 9. The mixed solutions of LMWOA and nZVI induced Pb(II) releases processes including a rapid desorption within 4 h and a slow desorption in the following hours. The second-order model was the most appropriate for describing the kinetic processes of Pb(II) desorption. The main fractions of Pb removal were exchangeable and reducible. Compared with LMWOA, the loss rates of nitrogen, phosphorus and potassium decreased after washing with the mixed solutions. Our study suggests that combining of LMWOA and nZVI would be a promising alternative approach for remediation Pb-contaminated soils. PMID:25461926

  10. 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

  11. 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

  12. 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

  13. Evaluation of the effects of nanoscale zero-valent iron (nZVI) dispersants on intrinsic biodegradation of trichloroethylene (TCE).

    PubMed

    Chang, Y C; Huang, S C; Chen, K F

    2014-01-01

    In this study, the biodegradability of nanoscale zero-valent iron (nZVI) dispersants and their effects on the intrinsic biodegradation of trichloroethylene (TCE) were evaluated. Results of a microcosm study show that the biodegradability of three dispersants followed the sequence of: polyvinyl alcohol-co-vinyl acetate-co-itaconic acid (PV3A) > polyoxyethylene (20) sorbitan monolaurate (Tween 20) > polyacrylic acid (PAA) under aerobic conditions, and PV3A > Tween 20 > PAA under anaerobic conditions. Natural biodegradation of TCE was observed under both aerobic and anaerobic conditions. No significant effects were observed on the intrinsic biodegradation of TCE under aerobic conditions with the presence of the dispersants. The addition of PAA seemed to have a slightly adverse impact on anaerobic TCE biodegradation. Higher accumulation of the byproducts of anaerobic TCE biodegradation was detected with the addition of PV3A and Tween 20. The diversity of the microbial community was enhanced under aerobic conditions with the presence of more biodegradable PV3A and Tween 20. The results of this study indicate that it is necessary to select an appropriate dispersant for nZVI to prevent a residual of the dispersant in the subsurface. Additionally, the effects of the dispersant on TCE biodegradation and the accumulation of TCE biodegrading byproducts should also be considered. PMID:24901632

  14. 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

  15. Removal of para-nitrochlorobenzene from aqueous solution on surfactant-modified nanoscale zero-valent iron/graphene nanocomposites.

    PubMed

    Wu, Yan; Luo, Hanjin; Wang, Hou

    2014-01-01

    This study demonstrated a remarkably simple and efficient method for the synthesis of nanoscale zero-valent iron (NZVI)/graphene (GN) nanocomposites. In order to prevent the agglomeration and restack of nanocomposites, chemical functionalization of nanocomposites with cetyltrimethylammonium bromide was proposed. The adsorption performance of surfactant-modified NZVI/GN nanocomposites was evaluated for the removal of para-nitrochlorobenzene (p-NCB) from aqueous solutions. The characteristics of nanocomposites were characterized by X-ray diffraction, BET surface area, Fourier transform infrared spectrum, thermogravimetric analysis and scanning electron microscopy. The effect factors including initial solution pH, contact time, reaction temperature, dosage, initial concentration of humic acid (HA) on the adsorption property of p-NCB onto surfactant-modified nanocomposites were investigated. The adsorption kinetics fitted well with pseudo-second-order model. The adsorption capacity of p-NCB on surfactant-modified nanocomposites inferred from the Langmuir model was 105.15 mg/g at 293 K. The thermodynamic parameters indicated that the adsorption of p-NCB onto surfactant-modified nanocomposites was an exothermic and spontaneous process. HA had a strong suppression effect on p-NCB uptake in the adsorption experiment. PMID:25176304

  16. 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

  17. Removal of EDTA from low pH printed-circuit board wastewater in a fluidized zero valent iron reactor.

    PubMed

    Chen, Shiao-Shing; Hsu, Hong-Der; Lin, Yi-Jiun; Chin, Pei-Ying

    2008-01-01

    Fluidized zero valent iron (ZVI) process was adopted to reduce ethylenediaminetetraacetic acid (EDTA) from low pH printed-circuit board (PCB) wastewater for two reasons: (1) low pH of the wastewater favoring the ZVI reaction; (2) higher ZVI utilization for fluidized process due to abrasive motion of the ZVI. The results showed that the degradation of EDTA was greatly enhanced under acidic pH, longer hydraulic detention time (HRT) and presence of dissolved oxygen (DO). Without addition of oxygen, 65% of EDTA was removed with capacity of 7.33 mg EDTA/g ZVI at pH 2, ZVI dosage of 424 g/L and HRT 10 min. With 6.8 mg/L of DO, 83% of EDTA was reduced with capacity of 19.01 mg EDTA/g ZVI for the same experimental condition. The presence of oxygen/ZVI initiated a Fenton type reaction to reduce EDTA. The end product after EDTA degradation was analyzed by high performance liquid chromoagraphy (HPLC), where propionic acid (C(2)H(5)COOH) was observed, indicating EDTA (oxidation number for carbon is 2) was oxidized to propionic acid (oxidation number for carbon is 3). Nitrogen species was also measured and the nitrogen in EDTA was converted to ammonium instead of nitrate and nitrite. PMID:18725736

  18. 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

  19. Passivation of zero-valent iron by denitrifying bacteria and the impact on trichloroethene reduction in groundwater.

    PubMed

    Chen, Liang; Jin, Song; Fallgren, Paul H; Liu, Fei; Colberg, Patricia J S

    2013-01-01

    Zero-valent iron (ZVI) application in groundwater remediation is limited by its vulnerability to passivation, which significantly decreases its surface reactivity. Both biological and chemical processes can potentially passivate ZVI, although the understanding of biological passivation is limited. This study was conducted in bench-scale reactors packed with fresh ZVI or ZVI pre-exposed to nitrate (NO3(-)) and in the presence or absence of a denitrifying bacterial enrichment (DNBE). The first-order rate coefficients (k) for NO3(-) reduction by ZVI in the presence and absence of DNBE were 0.20 and 0.09 s(-1), respectively, suggesting that both ZVI and microbes contribute to NO3(-) removal. Abiotic reduction of nitrate was observed in reactors with trichloroethene (TCE) if ZVI was present; however, it resulted in reduced rates of TCE reduction (k = 0.29 s(-1)) when compared to reactors with fresh ZVI and no nitrate (k = 0.55 s(-1)). The TCE reduction efficiency decreased by 49% (k = 0.15 s(-1)) in the presence of DNBE, suggesting that microbial growth on ZVI or catalyzed oxidation of ZVI surface can inhibit TCE reduction by ZVI. Contrary to the presumption that denitrification may decrease ZVI passivation by nitrate, results from this study suggest that denitrifying bacteria actually exacerbate ZVI passivation. PMID:23508149

  20. Fate of nitrogen species in nitrate reduction by nanoscale zero valent iron and characterization of the reaction kinetics.

    PubMed

    Hwang, Y H; Kim, D G; Ahn, Y T; Moon, C M; Shin, H S

    2010-01-01

    This study investigates the fate of nitrogen species during nitrate reduction by nanoscale zero valent iron (NZVI) as well as the related kinetics. The NZVI used for the experiments was prepared by chemical reduction without a stabilizing agent. The pseudo first order kinetic constant of nitrate reduction at 30 degrees C with an NZVI/nitrate ratio of 1.25:1, which were the reference conditions of this study, was 4.08 h(-1) (R(2)=0.955). A nitrogen mass balance was established by quantitative analysis of aqueous-phase and gas-phase nitrogen species. The results confirm that the nitrate was converted to ammonium ion, that ammonia stripping subsequently occurred under a strong alkaline condition, and that the total amount of aqueous nitrogen was consequently reduced. The nitrate reduction rate also increased with a lower pH and a higher temperature when microscale ZVI was used. However, in contrast to the reaction by microscale ZVI, the nitrate reduction rate by NZVI was higher for an unbuffered condition, possibly due to the abundance of surface atoms and the smaller size. PMID:20150707

  1. Decreasing ammonium generation using hydrogenotrophic bacteria in the process of nitrate reduction by nanoscale zero-valent iron.

    PubMed

    An, Yi; Li, Tielong; Jin, Zhaohui; Dong, Meiying; Li, Qianqian; Wang, Shuaima

    2009-10-15

    An integrated nitrate treatment using nanoscale zero-valent iron (NZVI) and Alcaligenes eutrophus, which is a kind of hydrogenotrophic denitrifying bacteria, was conducted to remove nitrate and decrease ammonium generation. Within 8 days, nitrate was removed completely in the reactors containing NZVI particles plus bacteria while the proportion of ammonium generated was only 33%. That is a lower reduction rate but a smaller proportion of ammonium relative to that in abiotic reactors. It was also found that ammonium generation experienced a biphasic process, involving an increasing period and a stable period. After domestication of the bacteria, the combined NZVI-cell system could remove all nitrate without ammonium released when the refreshed nitrate was introduced. Nitrate reduction and the final product distribution were also studied in batch reactors amended with different initial NZVI contents and biomass concentrations, respectively. Both the nitrate removal rate and the ammonium yield decreased when the initial content of NZVI reduced and the initial biomass concentration increased. However, about 27% of the nitrate was converted to ammonium when excess bacteria (OD(422)=0.026) were used, which was higher than that with appropriate amount of bacteria. PMID:19665759

  2. Effect of zero-valent iron on the start-up performance of anaerobic ammonium oxidation (anammox) process.

    PubMed

    Ren, Long-Fei; Ni, Shou-Qing; Liu, Cui; Liang, Shuang; Zhang, Bo; Kong, Qiang; Guo, Ning

    2015-02-01

    The long start-up time of anaerobic ammonium oxidation (anammox) process hinders the widespread application of anammox technology in practical wastewater treatment when anammox seed sludge is not available. Meanwhile, the production of nitrate cannot meet the increasingly more strict discharge standards. To combine the chemical nitrate reduction to ammonium with biological nitrogen removal, two anammox upflow anaerobic sludge blanket reactors packed with different types of zero-valent iron (ZVI), microscale ZVI (mZVI) and nanoscale ZVI (nZVI), were developed to accelerate the start-up of anammox process. The results revealed that anammox start-up time shortened from 126 to 105 and 84 days with the addition of mZVI and nZVI. The nitrogen removal performance was also improved remarkably by adding ZVI, especially in the start-up stage. The value of dissolved oxygen showed that ZVI could be regarded as a useful deoxidant to create anaerobic condition for the proliferation of anammox bacteria. ZVI was favorable for the secretion of EPS, which would represent the activity of anammox bacteria. The result of real-time quantitative PCR (qPCR) further confirmed that the proliferation of anammox bacteria was enhanced by ZVI. PMID:25226835

  3. Effects of nanoscale zero-valent iron particles on biological nitrogen and phosphorus removal and microorganisms in activated sludge.

    PubMed

    Wu, Donglei; Shen, Yanhong; Ding, Aqiang; Mahmood, Qaisar; Liu, Shuai; Tu, Qiaoping

    2013-11-15

    The use of nanoscale zero-valent iron (NZVI) particles in environmental remediation and wastewater treatment has recently increased. The effects of NZVI on nitrogen and phosphorus removal were examined under continuous aerobic/anaerobic conditions by employing activated sludge. NZVI did not display any measurable effect on nitrogen removal at the concentration of 50mg/L and below. However, 200mg/L of NZVI inhibited NH4(+)-N removal. The addition of NZVI at 20mg/L and above significantly (p<0.05) improved the phosphorous removal. The microbial activities were inhibited upon exposure to NZVI according to the ATP and reactive oxygen species (ROS) results. In comparison to control, the ATP content decreased by around 13%, 31% and 43% at the NZVI doses of 20, 50, and 200mg/L, respectively, probably due to ROS production under NZVI exposure. Lactate dehydrogenase (LDH) release assay suggested that NZVI concentration of 200mg/L cast adverse effects on microorganisms. Interestingly, lower concentrations of NZVI (20 and 50mg/L) boosted the dehydrogenase activity; however, approximately 19% depression in dehydrogenase activity was detected at 200mg/L. The high throughput 16S rDNA pyrosequencing results indicated that uncultured bacterial genera Sinobacteraceae, Xanthomonadaceae, Alcaligenaceae and Propionivibrio were sensitive to NZVI particles. PMID:24121637

  4. 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

  5. Zero-valent iron enhanced methanogenic activity in anaerobic digestion of waste activated sludge after heat and alkali pretreatment.

    PubMed

    Zhang, Yaobin; Feng, Yinghong; Quan, Xie

    2015-04-01

    Heat or alkali pretreatment is the effective method to improve hydrolysis of waste sludge and then enhance anaerobic sludge digestion. However the pretreatment may inactivate the methanogens in the sludge. In the present work, zero-valent iron (ZVI) was used to enhance the methanogenic activity in anaerobic sludge digester under two methanogens-suppressing conditions, i.e. heat-pretreatment and alkali condition respectively. With the addition of ZVI, the lag time of methane production was shortened, and the methane yield increased by 91.5% compared to the control group. The consumption of VFA was accelerated by ZVI, especially for acetate, indicating that the acetoclastic methanogenesis was enhanced. In the alkali-condition experiment, the hydrogen produced decreased from 27.6 to 18.8 mL when increasing the ZVI dosage from 0 to 10 g/L. Correspondingly, the methane yield increased from 1.9 to 32.2 mL, which meant that the H2-utilizing methanogenes was enriched. These results suggested that the addition of ZVI into anaerobic digestion of sludge after pretreated by the heat or alkali process could efficiently recover the methanogenic activity and increase the methane production and sludge reduction. PMID:25681947

  6. 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 adhering tendency of the corrosion products and not on the overall mass of corrosion products in the columns. The decrease in TCE reaction rates over time can be attributed to anodic control of iron corrosion and not to increasing reactant mass transfer limitations associated with diffusion through porous corrosion products.

  7. Identifying abiotic chlorinated ethene degradation: characteristic isotope patterns in reaction products with nanoscale zero-valent iron.

    PubMed

    Elsner, Martin; Chartrand, Michelle; Vanstone, Nancy; Couloume, Georges Lacrampe; Lollar, Barbara Sherwood

    2008-08-15

    Carbon isotope fractionation is of great interest in assessing chlorinated ethene transformation by nanoscale zero-valent iron at contaminated sites, particularly in distinguishing the effectiveness of an implemented abiotic degradation remediation scheme from intrinsic biotic degradation. Transformation of trichloroethylene (TCE), cis-dichloroethylene (cis-DCE), and vinyl chloride (VC) with two types of nanoscale iron materials showed different reactivity trends, but relatively consistent carbon isotope enrichment factors (epsilon) of -19.4 per thousand +/- 1.8 per thousand (VC), -21.7 per thousand +/- 1.8 per thousand (cis-DCE), and -23.5 per thousand +/- 2.8 per thousand (TCE) with one type of iron (FeBH), and from -20.9 per thousand +/- 1.1 per thousand to -26.5 per thousand +/- 1.5 per thousand (TCE) with the other (FeH2). Products of the dichloroelimination pathway (ethene, ethane, and acetylene) were consistently 10 per thousand more isotopically depleted than those of the hydrogenolysis pathway (cis-DCE from TCE, VC from cis-DCE), displaying a characteristic pattern that may serve as an indicator of abiotic dehalogenation reactions and as a diagnostic parameter for differentiating the effects of abiotic versus biotic degradation. In contrast, the product-related enrichment factors of each respective pathway varied significantly in different experiments. Because such variation would not be expected for independent pathways with constant kinetic isotope effects, our data give preliminary evidence that the two pathways may share an irreversible first reaction step with subsequent isotopically sensitive branching. PMID:18767652

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

    PubMed

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

    2015-01-01

    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. PMID:25827100

  9. 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.

  10. The limitations of applying zero-valent iron technology in contaminants sequestration and the corresponding countermeasures: the development in zero-valent iron technology in the last two decades (1994-2014).

    PubMed

    Guan, Xiaohong; Sun, Yuankui; Qin, Hejie; Li, Jinxiang; Lo, Irene M C; He, Di; Dong, Haoran

    2015-05-15

    Over the past 20 years, zero-valent iron (ZVI) has been extensively applied for the remediation/treatment of groundwater and wastewater contaminated with various organic and inorganic pollutants. Based on the intrinsic properties of ZVI and the reactions that occur in the process of contaminants sequestration by ZVI, this review summarizes the limitations of ZVI technology and the countermeasures developed in the past two decades (1994-2014). The major limitations of ZVI include low reactivity due to its intrinsic passive layer, narrow working pH, reactivity loss with time due to the precipitation of metal hydroxides and metal carbonates, low selectivity for the target contaminant especially under oxic conditions, limited efficacy for treatment of some refractory contaminants and passivity of ZVI arising from certain contaminants. The countermeasures can be divided into seven categories: pretreatment of pristine ZVI to remove passive layer, fabrication of nano-sized ZVI to increase the surface area, synthesis of ZVI-based bimetals taking advantage of the catalytic ability of the noble metal, employing physical methods to enhance the performance of ZVI, coupling ZVI with other adsorptive materials and chemically enhanced ZVI technology, as well as methods to recover the reactivity of aged ZVI. The key to improving the rate of contaminants removal by ZVI and broadening the applicable pH range is to enhance ZVI corrosion and to enhance the mass transfer of the reactants including oxygen and H(+) to the ZVI surface. The characteristics of the ideal technology are proposed and the future research needs for ZVI technology are suggested accordingly. PMID:25770444

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

    PubMed

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

    2014-03-01

    A field demonstration was conducted to assess the feasibility of nanoscale zero-valent iron (nZVI) for the treatment of wastewater containing high levels of Cu(II). Pilot tests were performed at a printed-circuit-board manufacturing plant, treating 250,000 L of wastewater containing 70 mg L(-1) Cu(II) with a total of 55 kg of nZVI. A completely mixed reactor of 1,600 L was operated continuously with flow rates ranging from 1000 to 2500 L h(-1). The average Cu(II) removal efficiency was greater than 96% with 0.20 g L(-1) nZVI and a hydraulic retention time of 100 min. The nZVI reactor achieved a remarkably high volumetric loading rate of 1876 g Cu per m(3) per day for Cu(II) removal, surpassing the loading rates of conventional technologies by more than one order of magnitude. The average removal capacity of nZVI for Cu(II) was 0.343 g Cu per gram of Fe. The Cu(II) removal efficiency can be reliably regulated by the solution Eh, which in turn is a function of nZVI input and hydraulic retention time. The ease of separation and recycling of nZVI contribute to process up-scalability and cost effectiveness. Cu(II) was reduced to metallic copper and cuprite (Cu2O). The end product is a valuable composite of iron and copper (?20-25%), which can partially offset the treatment costs. PMID:24473735

  12. 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 1h. 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

  13. 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

  14. Enhanced degradation of trichloroethylene in nano-scale zero-valent iron Fenton system with Cu(II).

    PubMed

    Choi, Kyunghoon; Lee, Woojin

    2012-04-15

    Degradation of trichloroethylene (TCE) in nano-scale zero-valent iron (nZVI) Fenton system with Cu(II) was investigated in a closed batch system. TCE was significantly degraded (95%) in 10 min in nZVI Fenton system with 20mM Cu(II) at initial pH 3, while slight degradation (25%) was observed in nZVI Fenton system without Cu(II) at the same experimental condition. Aqueous Fe(II) concentration proportionally increased (1.2-19.6mM) with increasing Cu(II) concentration (1-20mM). Surface analyses using X-ray spectroscopy showed that metallic Cu was formed on the nZVI surface and surface Fe(0) decreased by 1.4 times after the addition of Cu(II) to nZVI suspension. Kinetic rate constant for TCE degradation at 15.3mM nZVI (4.1989 min(-1)) increased by 1.8 times till the increase of nZVI concentration by 5 times and then showed a saturation pattern at higher nZVI concentration. As Cu(II) concentrations increased in the Cu/nZVI Fenton system, the rate constant increased linearly (R(2)=0.979). No significant difference has been observed in the degradation kinetics of TCE by Cu/nZVI Fenton at pH 3 and pH 6 (4.8720 min(-1) vs. 4.9858 min(-1)), whereas the kinetics by nZVI Fenton at pH 6 were 1.6 times faster (0.0318 min(-1)) than at pH 3 (0.0194 min(-1)). PMID:22079185

  15. Comparative studies on montmorillonite-supported zero-valent iron nanoparticles produced by different methods: reactivity and stability.

    PubMed

    Jia, Hanzhong; Wang, Chuanyi

    2013-01-01

    To mitigate the aggregation and enhance the reactivity of nanosized zero-valent iron (nZVI), montmorillonite is employed as a template-supporting matrix to prepare nZVI through two different pathways: heterogeneous nucleation and homogeneous nucleation processes. Dispersed sub-nanosized ZVI clusters with an average size around 0.5 nm (perpendicular to the clay layers) are intercalated in clay interlayers when using montmorillonite as a template in preparation via heterogeneous nucleation process. However, the particle sizes spanned from 0.62 nm (perpendicular to the clay layers) for the ZV1 intercalated in montmorillonite interlayers to 1-50 nm for the ZVI residing on an external surface when using montmorillonite as a dispersion agent in the preparation via homogeneous nucleation. Furthermore, parallel batch experiments have been conducted with nZVIs synthesized by the two different methods in solutions of nitrobenzene and their reactivity is evaluated via response of nZVI to nitrobenzene remediation. As a result, the reactivity of ZVI synthesized by heterogeneous nucleation is greater than that by homogeneous nucleation, which is inversely correlated to the size of ZVI supported by montmorillonite clay. Evaluation of the stability of montmorillonite-supported ZVI showed that ZVI intercalated in the interlayers of montmorillonite is more stable than that located on the external surface, which can be attributed to the protective effect of montmorillonite layers on ZVI from oxidation. These results suggest that the great reactivity and high stability of montmorillonite-intercalated ZVI synthesized through heterogeneous nucleation process warrants its significant potential in developing in situ remediation and treatment technologies for organic contaminants. PMID:23530312

  16. Microbial community response of nitrifying sequencing batch reactors to silver, zero-valent iron, titanium dioxide and cerium dioxide nanomaterials.

    PubMed

    Ma, Yanjun; Metch, Jacob W; Vejerano, Eric P; Miller, Ian J; Leon, Elena C; Marr, Linsey C; Vikesland, Peter J; Pruden, Amy

    2015-01-01

    As nanomaterials in consumer products increasingly enter wastewater treatment plants, there is concern that they may have adverse effects on biological wastewater treatment. Effects of silver (nanoAg), zero-valent iron (NZVI), titanium dioxide (nanoTiO?) and cerium dioxide (nanoCeO?) nanomaterials on nitrification and microbial community structure were examined in duplicate lab-scale nitrifying sequencing batch reactors (SBRs) relative to control SBRs that received no nanomaterials or ionic/bulk analogs. Nitrification function was not measurably inhibited in the SBRs by any of the materials as dosing was initiated at 0.1 mg/L and sequentially increased every 14 days to 1, 10, and 20 mg/L. However, SBRs rapidly lost nitrification function when the Ag? experiment was repeated at a continuous high load of 20 mg/L. Shifts in microbial community structure and decreased microbial diversity were associated with both sequential and high loading of nanoAg and Ag?, with more pronounced effects for Ag?. Bacteroidetes became more dominant in SBRs dosed with Ag?, while Proteobacteria became more dominant in SBRs dosed with nanoAg. The two forms of silver also had distinct effects on specific bacterial genera. A decrease in nitrification gene markers (amoA) was observed in SBRs dosed with nanoAg and Ag?. In contrast, impacts of NZVI, nanoTiO?, nanoCeO? and their analogs on microbial community structure and nitrification gene markers were limited. TEM-EDS analysis indicated that a large portion of nanoAg remained dispersed in the activated sludge and formed AgS complexes, while NZVI, nanoTiO? and nanoCeO? were mostly aggregated and chemically unmodified. Overall, this study suggests a high threshold of the four nanomaterials in terms of exerting adverse effects on nitrification function. However, distinct microbial community responses to nanoAg indicate potential long-term effects. PMID:25462719

  17. Applying an electric field in a built-in zero valent iron--anaerobic reactor for enhancement of sludge granulation.

    PubMed

    Liu, Yiwen; Zhang, Yaobin; Quan, Xie; Chen, Shuo; Zhao, Huimin

    2011-01-01

    A zero valent iron (ZVI) bed with a pair of electrodes was installed in an upflow anaerobic sludge blanket (UASB) reactor to create an enhanced condition to increase the rate of anaerobic granulation. The effects of an electric field and ZVI on granulation were investigated in three UASB reactors operated in parallel: an electric field enhanced ZVI-UASB reactor (reactor R1), a ZVI-UASB reactor (reactor R2) and a common UASB reactor (reactor R3). When a voltage of 1.4 V was supplied to reactor R1, COD removal dramatically increased from 60.3% to 90.7% over the following four days, while the mean granule size rapidly grew from 151.4 ?m to 695.1 ?m over the following 38 days. Comparatively, COD removal was lower and the increase in granule size was slower in the other two reactors (in the order: R1 > R2 > R3). The electric field caused the ZVI to more effectively buffer acidity and maintain a relatively low oxidation-reduction potential in the reactor. In addition, the electric field resulted in a significant increase in ferrous ion leaching and extracellular polymeric substances (EPS) production. These changes benefited methanogenesis and granulation. Scanning electron microscopy (SEM) images showed that different microorganisms were dominant in the external and internal layers of the reactor R1 granules. Additionally, fluorescence in situ hybridization (FISH) analysis indicated that the relative abundance of methanogens in reactor R1 was significantly greater than in the other two reactors. Taken together, these results suggested that the use of ZVI combined with an electric field in an UASB reactor could effectively enhance the sludge granulation. PMID:20965541

  18. 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.

  19. Graphene-supported nanoscale zero-valent iron: removal of phosphorus from aqueous solution and mechanistic study.

    PubMed

    Liu, Fenglin; Yang, JingHe; Zuo, Jiane; Ma, Ding; Gan, Lili; Xie, Bangmi; Wang, Pei; Yang, Bo

    2014-08-01

    Excess phosphorus from non-point pollution sources is one of the key factors causing eutrophication in many lakes in China, so finding a cost-effective method to remove phosphorus from non-point pollution sources is very important for the health of the aqueous environment. Graphene was selected to support nanoscale zero-valent iron (nZVI) for phosphorus removal from synthetic rainwater runoff in this article. Compared with nZVI supported on other porous materials, graphene-supported nZVI (G-nZVI) could remove phosphorus more efficiently. The amount of nZVI in G-nZVI was an important factor in the removal of phosphorus by G-nZVI, and G-nZVI with 20 wt.% nZVI (20% G-nZVI) could remove phosphorus most efficiently. The nZVI was very stable and could disperse very well on graphene, as characterized by transmission electron microscopy (TEM) and scanning electron microscopy (SEM). X-ray photoelectron spectroscopy (XPS), Fourier Transform infrared spectroscopy (FT-IR) and Raman spectroscopy were used to elucidate the reaction process, and the results indicated that Fe-O-P was formed after phosphorus was adsorbed by G-nZVI. The results obtained from X-ray diffraction (XRD) indicated that the reaction product between nZVI supported on graphene and phosphorus was Fe?(PO?)?8H?O (Vivianite). It was confirmed that the specific reaction mechanism for the removal of phosphorus with nZVI or G-nZVI was mainly due to chemical reaction between nZVI and phosphorus. PMID:25108732

  20. 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 0.5g/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 0.05g/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

  1. A heterogeneous Fenton-like system with nanoparticulate zero-valent iron for removal of 4-chloro-3-methyl phenol.

    PubMed

    Xu, Lejin; Wang, Jianlong

    2011-02-15

    The removal of biocide 4-chloro-3-methyl phenol (CMP) was investigated by heterogeneous Fenton-like system using nanoparticulate zero-valent iron (nZVI) as catalyst. The properties of nZVI before and after reaction were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The effects of pH value, initial concentration of CMP, nZVI dose and hydrogen peroxide (H(2)O(2)) concentration were determined. The experimental results showed that lower pH value and CMP concentration brought faster degradation rate. With the initial pH value of 6.1 and initial CMP concentration of 0.7 mM, the optimal dosage of reagents were 0.5 g nZVI/L and 3.0 mM H(2)O(2). At pH 6.1, the degradation of CMP followed two-stage first-order kinetic that composed of an induction period (first-stage) and a followed rapid degradation stage (second-stage). According to the effects of scavengers n-butanol and KI, hydroxyl radicals (OH), especially the surface-bounded OH, had a dominant role in the oxidation of CMP. The degradation intermediates, carboxylic acids and chloride ion produced during the reaction process were monitored by high performance liquid chromatography (HPLC), liquid chromatography/mass spectrometry (LC/MS) and ion chromatography (IC). On the basis of these findings, the possible mechanistic steps of CMP degradation were proposed. PMID:21109349

  2. Effect of natural organic matter on toxicity and reactivity of nano-scale zero-valent iron.

    PubMed

    Chen, Jiawei; Xiu, Zongming; Lowry, Gregory V; Alvarez, Pedro J J

    2011-02-01

    Nano-scale zero-valent iron (NZVI) particles are increasingly used to remediate aquifers contaminated with hazardous oxidized pollutants such as trichloroethylene (TCE). However, the high reduction potential of NZVI can result in toxicity to indigenous bacteria and hinder their participation in the cleanup process. Here, we report on the mitigation of the bactericidal activity of NZVI towards gram-negative Escherichia coli and gram-positive Bacillus subtilis in the presence of Suwannee River humic acids (SRHA), which were used as a model for natural organic matter (NOM). B. subtilis was more tolerant to NZVI (1 g/L) than E. coli in aerobic bicarbonate-buffered medium. SRHA (10 mg/L) significantly mitigated toxicity, and survival rates after 4 h exposure increased to similar levels observed for controls not exposed to NZVI. TEM images showed that the surface of NZVI and E. coli was surrounded by a visible floccus. This decreased the zeta potential of NZVI from -30 to -45 mV and apparently exerted electrosteric hindrance to minimize direct contact with bacteria, which mitigated toxicity. H(2) production during anaerobic NZVI corrosion was not significantly hindered by SRHA (p > 0.05), However, NZVI reactivity towards TCE (20 mg/L), assessed by the first-order dechlorination rate coefficient, decreased by 23%. Overall, these results suggest that the presence of NOM offers a tradeoff for NZVI-based remediation, with higher potential for concurrent or sequential bioremediation at the expense of partially inhibited abiotic reactivity with the target contaminant (TCE). PMID:21232782

  3. PCE dissolution and simultaneous dechlorination by nanoscale zero-valent iron particles in a DNAPL source zone.

    PubMed

    Fagerlund, F; Illangasekare, T H; Phenrat, T; Kim, H-J; Lowry, G V

    2012-04-01

    While the capability of nanoscale zero-valent iron (NZVI) to dechlorinate organic compounds in aqueous solutions has been demonstrated, the ability of NZVI to remove dense non-aqueous phase liquid (DNAPL) from source zones under flow-through conditions similar to a field scale application has not yet been thoroughly investigated. To gain insight on simultaneous DNAPL dissolution and NZVI-mediated dechlorination reactions after direct placement of NZVI into a DNAPL source zone, a combined experimental and modeling study was performed. First, a DNAPL tetrachloroethene (PCE) source zone with emplaced NZVI was built inside a small custom-made flow cell and the effluent PCE and dechlorination byproducts were monitored over time. Second, a model for rate-limited DNAPL dissolution and NZVI-mediated dechlorination of PCE to its three main reaction byproducts with a possibility for partitioning of these byproducts back into the DNAPL was formulated. The coupled processes occurring in the flow cell were simulated and analyzed using a detailed three-dimensional numerical model. It was found that subsurface emplacement of NZVI did not markedly accelerate DNAPL dissolution or the DNAPL mass-depletion rate, when NZVI at a particle concentration of 10g/L was directly emplaced in the DNAPL source zone. To react with NZVI the DNAPL PCE must first dissolve into the groundwater and the rate of dissolution controls the longevity of the DNAPL source. The modeling study further indicated that faster reacting particles would decrease aqueous contaminant concentrations but there is a limit to how much the mass removal rate can be increased by increasing the dechlorination reaction rate. To ensure reduction of aqueous contaminant concentrations, remediation of DNAPL contaminants with NZVI should include emplacement in a capture zone down-gradient of the DNAPL source. PMID:22326687

  4. 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%.

  5. 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

  6. 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

  7. 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.

  8. 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).

  9. Humic acid aggregation in zero-valent iron systems and its effects on trichloroethylene removal.

    PubMed

    Tsang, Daniel C W; Graham, Nigel J D; Lo, Irene M C

    2009-06-01

    The influence of natural organic matter on contaminant removal by Fe(0) systems has been of increasing concern. Recent studies have shown that, in addition to direct sorption on the Fe(0) surfaces, humic acid complexation with dissolved iron released from corrosion results in the formation of colloids and aggregates in solution that may affect contaminant removal. High-pressure size-exclusion chromatographic analyses revealed increasing molecular weights of dissolved humic acids with reaction time. Humic acid aggregation occurred across a wide range of molecular weight fractions. Fourier transform infrared spectroscopic analysis of humic acid aggregates suggested the presence of inner-sphere complexation involving different oxygen-containing functional groups; hydrophobic interactions also probably contributed to aggregation as the humic acid of more aromatic and hydrophobic character was aggregated at a faster rate. Because of multiple underlying processes, a variety of cross-correlated physicochemical properties of humic acids contributed to their aggregation. The presence of humic acid aggregates provided an additional hydrophobic domain for partitioning that enhanced trichloroethylene removal, although steric blocking of the Fe(0) surfaces may inhibit its reduction to some extent. Comparable effects were demonstrated for various types of humic acids. PMID:19327814

  10. Performance of a zero valent iron-based anaerobic system in swine wastewater treatment.

    PubMed

    Wu, Donglei; Zheng, Shuangshuang; Ding, Aqiang; Sun, Guodong; Yang, Meiqing

    2015-04-01

    In this paper, short-term exposure experiments with different ZVI concentrations were conducted to research the effects of ZVI adding on the anaerobic system for treating swine wastewater. Increasing the ZVI dose had a stimulatory effect on COD removal and CH4 production possibly due to a higher corrosion-induced H2 and dissolved ferrous ions, which could stimulate the methanogenesis and thus the biodegradation. In addition, the abiotic corrosion reactions such as flocculation, adsorption and precipitation were inevitable to removal some suspended COD. However, high ZVI doses had a potential risk on microorganism due to the present of large numbers of solid iron species in sludge, which likely encapsulated the cells and even damaged the cellular structure. Taken as a whole, the most enhancing effect induced by ZVI was observed at the rZVI/VSS of 2.63, and the maximum efficiency of per ZVI adding occurred at the rZVI/VSS of 0.74. But the ZVI concentration of 50 g/L (the rZVI/VSS was 5.26) was proved too high to facilitate microorganism activity, considering the higher LDH leakage and lower intracellular ATP level than the only sludge system. PMID:25543891

  11. Polyoxometalate-Enhanced Oxidation of Organic Compounds by Nanoparticulate Zero-Valent Iron and Ferrous Ion in the Presence of Oxygen

    PubMed Central

    Lee, Changha; Keenan, Christina R.; Sedlak, David L.

    2008-01-01

    In the presence of oxygen, organic compounds can be oxidized by zero-valent iron or dissolved Fe(II). However, this process is not a very effective means of degrading contaminants because the yields of oxidants are usually low (i.e., typically less than 5% of the iron added is converted into oxidants capable of transforming organic compounds). The addition of polyoxometalate (POM) greatly increases the yield of oxidants in both systems. The mechanism of POM enhancement depends on solution pH. Under acidic conditions, POM-mediates the electron transfer from nanoparticulate zero-valent iron (nZVI) or Fe(II) to oxygen, increasing the production of hydrogen peroxide, which is subsequently converted to hydroxyl radical through the Fenton reaction. At neutral pH values, iron forms a complex with POM, preventing iron precipitation on the nZVI surface and in bulk solution. At pH 7, the yield of oxidant approaches the theoretical maximum in the nZVI/O2 and the Fe(II)/O2 systems when POM is present, suggesting that coordination of iron by POM alters the mechanism of the Fenton reaction by converting the active oxidant from ferryl ion to hydroxyl radical. Comparable enhancements in oxidant yields are also observed when nZVI or Fe(II) are exposed to oxygen in the presence of silica-immobilized POM. PMID:18678027

  12. Environmental benefits and risks of zero-valent iron nanoparticles (nZVI): risk mitigation or trade-off?

    NASA Astrophysics Data System (ADS)

    Grieger, K.; Fjordbge, A.; Hartmann, N.; Eriksson, E.; Baun, A.

    2009-12-01

    The use of nanoscaled particles in environmental remediation is gaining increasing amounts of attention in recent years, including the use of zero-valent iron nanoparticles (nZVI) for soil and groundwater remediation. The main advantages of its use include high degrees of reactivity towards a wide range of contaminants, enhanced mobility of the often coated particles, and its cost-effective in situ applications. Numerous studies have shown that compared to larger sized iron particles nZVI may have some superior properties, due to high surface areas and small sizes associated with nanoscale dimensions. While the use and further development of nZVI is understandably heralded as an environmentally-beneficial technology, the potentials risks of introducing these nanoparticles into the environment also needs to be considered. To date most research has focused on the potential benefits of nZVI and very little research has investigated its potential health and environmental risks. Nonetheless, some recent studies have documented adverse effects from its exposure including the generation of reactive oxygen species (ROS), oxidative stress, bactericidal effects, DNA damage, and inflammatory responses. Moreover, field site injections often involve the use of large quantities of nZVI (10-50 g/L) which may be directly injected into groundwater flow. Combined with the pursuit of designing more mobile and reactive particles, this may potentially lead to risks related to environmental exposures of substantial concentrations. In this study, we provide a brief synopsis of the expected environmental benefits and potential risks of nZVI, particularly focusing on its environmental fate and behavior and potential role as contaminant carrier. These are some areas of primary concern for risk assessors. Furthermore, we estimate and compare the span between probable environmental concentrations from its use in the field and concentrations which have been shown to cause adverse effects in laboratory settings. This is in light of the challenges that quantitative risk assessments face for nZVI and other nanoparticles, in part due to extensive and fundamental uncertainties. These data may provide a starting point to more thoroughly investigate the potential risks of nZVI and ultimately help scientists, engineers, and decision makers make better informed decisions regarding the use of nZVI for environmental remediation.

  13. 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 soil, the presence of SDS at sub-cmc increased TCE degraded by {approx}10%. However, effect of SDS on degradation of TCE in the potting soil was more complex. The presence of SDS at sub-cmc decreased TCE degradation by 5%, but increased degradation by 5% when SDS dosage was raised to 5 x cmc. The opposing effects were attributed to combined effects of SDS on TCE desorption and degradation, release of soil organic matter and nanoparticle aggregation. The findings strongly suggest that effect of soil sorption on the effectiveness of Fe-Pd nanoparticles must be taken into account in process design, and soil organic content plays an important role in the overall degradation rate and in the effectiveness of surfactant uses.

  14. 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 (3g/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 (2.30נ10(-3)m/s) within the coarsest porous media (0.8-1.2mm), 86.52% of the XG-mZVI flowed through the column. At the lowest flow rate (0.97נ10(-4)m/s) within the finest porous media (0.3-0.6mm), 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 maximizing the radius of influence of the injection and minimizing the injection pressure. PMID:26497937

  15. 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 between 2.6×10(-4) and 5.7×10(-4)Lm(-2)h(-1). Our results revealed that the easy-to-handle and air-stable Nanofer Star particles are the least reactive of all the Nanofer products tested. The reaction kinetics predicted by column experiments were more realistic than those predicted by batch experiments and these should therefore be used when designing a full-scale field application of nanomaterials for environmental remediation. PMID:25708601

  16. Nitrate reduction using nanosized zero-valent iron supported by polystyrene resins: role of surface functional groups.

    PubMed

    Jiang, Zhenmao; Lv, Lu; Zhang, Weiming; Du, Qiong; Pan, Bingcai; Yang, Lei; Zhang, Quanxing

    2011-03-01

    To probe the role of host chemistry in formation and properties of the inside nano-zero valent iron (nZVI), we encapsulated nZVI within porous polystyrene resins functionalized with -CH(2)Cl and -CH(2)N(+)(CH(3))(3) respectively and obtained two hybrid nZVIs denoted Cl-S-ZVI and N-S-ZVI. 14.5% (in Fe mass) of nZVI particles were distributed in N-S within a ring-like region (about 0.10 mm in thickness) of size around ∼ 5 nm, whereas only 4.0% of nZVI particles were entrapped near the outer surface of Cl-S of size > 20 nm. -CH(2)N(+)(CH(3))(3) is more favorable than -CH(2)Cl to inhibit nZVI dissolution into Fe(2+) ions under acidic pH (3.0-5.5). 97.2% of nitrate was converted into ammonium when introducing 0.12 g N-S-ZVI into 50 mL 50 mg N/L nitrate solution, while that for Cl-S-ZVI was 79.8% under identical Fe/N molar ratio. Under pH = 2 of the effectiveness of nZVI was 88.8% for nitrate reduction, whereas that for Cl-S-ZVI was only 14.6% under similar conditions. Nitrate reduction by N-S-ZVI exhibits relatively slower kinetics than Cl-S-ZVI, which may be related to different nZVI distribution of both composites. The coexisting chloride and sulfate co-ions are favorable for the reactivity enhancement of N-S-ZVI whereas slightly unfavorable for Cl-S-ZVI. The results demonstrated that support chemistry plays a significant role in formation and reactivity of the encapsulated nZVI, and may shed new light on design and fabrication of hybrid nZVIs for environmental remediation. PMID:21316071

  17. 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 practical importance for understanding the process of dechlorination in the presence of multiple OCPs and the development of remediation techniques for the soils contaminated by OCPs. PMID:20471666

  18. 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

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

    PubMed

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

    2002-05-01

    Three treatment cells were operated at a site near Durango, CO. One treatment cell operated for more than 3 years. The treatment cells were used for passive removal of contamination from groundwater at a uranium mill tailings repository site. Zero-valent iron [Fe(0)] that had been powdered, bound with aluminosilicate and molded into plates was used as a reactive material in one treatment cell. The others used granular Fe(0) and steel wool. The treatment cells significantly reduced concentrations of As, Mn, Mo, Se, U, V and Zn in groundwater that flowed through it. Zero-valent iron [Fe(0)], magnetite (Fe3O4), calcite (CaCO3), goethite (FeOOH) and mixtures of contaminant-bearing phases were identified in the solid fraction of one treatment cell. A reaction progress approach was used to model chemical evolution of water chemistry as it reacted with the Fe(0). Precipitation of calcite, ferrous hydroxide [Fe(OH)2] and ferrous sulfide (FeS) were used to simulate observed changes in major-ion aqueous chemistry. The amount of reaction progress differed for each treatment cell. Changes in contaminant concentrations were consistent with precipitation of reduced oxides (UO2, V2O3), sulfides (As2S3, ZnS), iron minerals (FeSe2, FeMoO4) and carbonate (MnCO3). Formation of a free gas phase and precipitation of minerals contributed to loss of hydraulic conductivity in one treatment cell. PMID:12076025

  20. Injection of Nano Zero-Valent Iron for Subsurface Remediation: Evaluation of Methods for Assessment of Nanoparticle Delivery (Invited)

    NASA Astrophysics Data System (ADS)

    Tratnyek, P. G.; Shi, Z.; Nurmi, J. T.; Johnson, R. L.

    2010-12-01

    Among emerging technologies for in situ remediation of subsurface contamination, injection of nano-sized zero-valent iron (nZVI) stands out for the sudden growth in interest it has attracted. Field scale applications of this technology exist for a variety of types of sites, and most of these projects have been described as being successful. None of these sites have been extensively characterized, however, and there is not yet a critical mass of field data on which to make generalizations about the performance of nZVI-based remediation technologies. Furthermore, some aspects of the reported field results are not easily reconciled with results of laboratory and modeling studies of nZVI properties and behavior. Clearly, a more thorough and rigorous understanding of this system is needed to ensure that applications of this technology are successful. Among the critical issues to be addressed, detection of iron nanoparticles remains a challenge, and there is no established protocol for detecting iron nanoparticles in the field upon nZVI injection. Oxidation-reduction potential (ORP) measurements have been widely used to assess the results of injection of nZVI for groundwater remediation. However, the significance of such measurements is unclear because the complex interaction between the target materials (e.g. suspensions of highly reactive and variably aggregated nanoparticles) and the electrode has never been characterized. In recent work, we have investigated the effect of nZVI on ORP measurements under various reaction conditions. The electrochemical techniques used include chronopotentiometry and linear-sweep voltammetry with traditional stationary disc electrodes (SDEs), rotating disc electrodes (RDEs), and flow-through cell disc electrodes (FDEs). From ORP measurements in suspensions of nZVI, we found the electrode response to be highly complex, but also a very sensitive probe for a range of fundamentally significant processes. The ORP measurements of nZVI suspensions with both SDEs and RDEs indicate that the interaction of iron nanoparticles with the working electrode significantly contributed to the working electrode response, which is complicated by the solution chemistry and particle properties. The time dependence of the electrode response reflects both a primary effect (sorption of nZVI on the electrode surface) and secondary effects (via Fe oxidation and dissolved H2) of nZVI on ORP. Organic coatings on nZVI particles reduced the primary effect of nZVI by protecting the particle and electrode surfaces. Oxidation of nZVI resulted in rebound of the ORP, as indicated by a progressive shift of the corrosion potential (Ecorr) to more positive values obtained from LSV measurements. Combinations of electrochemical and other methods will be needed to differentiate particle concentration, composition, and reactivity after nZVI injection into the subsurface environment.

  1. 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.

  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 ?m to 425 ?m 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 effect on velocity and nZVI attachment. The transport experiments are being modeled using a two-dimensional multiphase flow and transport model. The sandbox is being discretized into 55 by 45 grid blocks (1 cm x 1 cm x 1.3 cm in size). LGB and CMC are modeled as soluble components, while nZVI is being considered as a colloid. In case of nZVI transport, attachment coefficients are being fitted to match the experimental breakthrough curves. The estimated attachment coefficients can be used to predict the CMC stabilized nZVI transport in field scale applications.

  3. 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

  4. 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...

  5. Removal of selenite by zero-valent iron combined with ultrasound: Se(IV) concentration changes, Se(VI) generation, and reaction mechanism.

    PubMed

    Fu, Fenglian; Lu, Jianwei; Cheng, Zihang; Tang, Bing

    2016-03-01

    In this paper, the performance and application of zero-valent iron (ZVI) assisted by ultrasonic irradiation for the removal of selenite (Se(IV)) in wastewater was evaluated and reaction mechanism of Se(IV) with ZVI in such systems was investigated. A series of batch experiments were conducted to determine the effects of ultrasound power, pH, ZVI concentration, N2 and air on Se(IV) removal. ZVI before and after reaction with Se(IV) was characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). Results indicated that ultrasound can lead to a significant synergy in the removal of Se(IV) by ZVI because ultrasound can promote the generation of OH and accelerate the advanced Fenton process. The primary reaction products of ZVI and Se(IV) were Se(0), ferrihydrite, and Fe2O3. PMID:26585013

  6. 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

  7. A column study of geochemical factors affecting reductive dechlorination of chlorinated solvents by zero-valent iron

    SciTech Connect

    Johnson, T.L.; Tratnyek, P.G.

    1994-12-31

    Laboratory and field studies have shown that fillings of metal that are predominantly Fe{sup 0} can rapidly dehalogenate a variety of chlorinated solvents, and several technologies have recently been proposed to use this reaction in remediation of contaminated ground water. This report describes results from a laboratory column designed to model the spatial distribution of chemical conditions when iron is applied as part of an in-situ permeable reactive barrier. The column contains a zone of granular iron located between up-gradient and down-gradient zones of sand, and has received deionized water with varying concentrations of CCl{sub 4} for over 6 months. Aerobic corrosion results in complete consumption of dissolved oxygen and precipitation of ferric hydroxides at the interface where water enters the iron-bearing zone. Within the iron-bearing zone, corrosion continues due to oxidation of the iron by water and carbon tetrachloride, resulting in increased pH and concentration of dissolved iron in the pore water. At the down-gradient interface, pH decreased as the result of precipitation of iron-bearing minerals. Carbon tetrachloride (up to 1.6 mM) was fully dehalogenated by the first sample port within the iron-bearing zone. The chloroform produced was further dechlorinated to dichloromethane, but at a slower rate. First-order disappearance kinetics for chloroform applied across the zone of iron, and k{sub obs} has changed little over several months. No evidence has been found so far for unusual reactivity of the chlorinated solvents at either the up-gradient or down-gradient interfaces.

  8. Influence of solution composition and column aging on the reduction of nitroaromatic compounds by zero-valent iron.

    PubMed

    Klausen, J; Ranke, J; Schwarzenbach, R P

    2001-08-01

    Granular iron is used in reactive permeable barriers for the reductive treatment of organic and inorganic groundwater contaminants. The technology is well established, however, its long-term performance and the importance of the groundwater composition are not yet well understood. Here, the influence of chloride, nitrate, silicate, and Aldrich humic acid on the reactivity of Master Builder iron was studied under anoxic conditions using small packed columns and 2-nitrotoluene (2-NT) as a model contaminant. After initially complete reduction of 2-NT to 2-aminotoluene (2-AT) in the column, possibly under mass-transfer controlled conditions, the reactivity of the iron was found to decrease substantially. In the presence of chloride, this decrease was slowed while exposure to silicate resulted in a very quick loss of iron reactivity. Nitrate was found to interfere strongly with the effect of chloride. These observations are interpreted in terms of corrosion inhibition/promotion and competition. Our results suggest that reactive barrier performance may be strongly affected by the composition of the treated groundwater. PMID:11482637

  9. 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

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

    PubMed

    Krinik, Nina; Mladenovi?, Ana; kapin, Andrijana Sever; krlep, Luka; ?an?ar, Janez; Mila?i?, 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

  11. Effect of the addition of zero valent iron (Fe(0)) on the batch biological sulphate reduction using grass cellulose as carbon source.

    PubMed

    Mulopo, Jean; Schaefer, L

    2013-12-01

    Mineral mining generates acidic, saline, metal-rich mine waters, often referred to as acid mine drainage (AMD). Treatment of AMD and recovering saleable products during the treatment process are a necessity since water is, especially in South Africa, a scarce commodity. The aim of the study presented here was to investigate the effect of zero valent iron (Fe(0)) on the biological removal of sulphate from AMD in batch reactors. The performance of the reactors was assessed by means of sulphate reduction, chemical oxygen demand (COD), volatile fatty acid (VFA) utilisation and volatile suspended solids (VSS) concentration. To this end, three batch reactors, A, B and C (volume 2.5 L), were operated similarly with the exception of the addition of grass cuttings and iron filings. Reactors A and B received twice as much grass (100 g) as C (50 g). Reactor A received no iron filings to act as a control, while reactors B and C received 50-g iron filings for the experimental duration. The results showed that Fe(0) appears to provide sustained sulphate removal when sufficient grass substrate is available. In reactors A and C, sulphate removal efficiency was higher when the COD concentration was lower due to utilisation. In reactor B, sulphate removal efficiency was accompanied by an accumulation of COD as hydrogen (H2) provided by the Fe(0) was utilised for sulphate reduction. Furthermore, these results showed the potential of Fe(0) to enhance the participation of microorganisms in sulphate reduction. PMID:24018847

  12. Reductive removal of selenate by zero-valent iron: The roles of aqueous Fe(2+) and corrosion products, and selenate removal mechanisms.

    PubMed

    Tang, Cilai; Huang, Yong H; Zeng, Hui; Zhang, Zengqiang

    2014-12-15

    Batch tests were conducted to investigate the roles of dissolved Fe(2+) and corrosion products, and the involved mechanisms in selenate (Se(VI)) removal by zero-valent iron (ZVI). The results showed that insignificant Se(VI) removal (4-7.5%) was observed in the presence of ZVI or Fe(2+) alone. However, external supply of dissolved ferrous ion dramatically enhanced Se(VI) removal in the presence of ZVI. Selenate removal efficiency increased with increasing Fe(2+) concentration. Selenate removal sustained only if Fe(2+) was supplied continuously. Both sequential extraction experiments and XPS analysis showed that selenate was reduced step by step, with elemental selenium and adsorbed selenite as the dominant reductive products. Selenite and elemental selenium could be further reduced to selenide, with continuous Fe(2+) supply and sufficient reaction time. In the ZVI-Se(VI)-Fe(2+) system, ZVI was the major electron donor for selenate reduction. Fe(2+) functioned as electron donor as well and was consumed with a Fe(2+):Se stoichiometry of ?1:1. It also facilitated the transformation of the passive layer of iron coatings to a medium (e.g., magnetite) favoring electron transfer and thus enhanced selenate reduction. Iron corrosion products were media for electron transfer and reactive interfaces for selenium adsorption and reduction. These findings provided a new approach to overcome ZVI surface passivation for long-term application. PMID:25269108

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

    PubMed

    Liu, Airong; Zhang, Wei-xian

    2014-09-21

    An angstrom-resolution physical model of nanoscale zero-valent iron (nZVI) is generated with a combination of spherical aberration corrected scanning transmission electron microscopy (Cs-STEM), selected area electron diffraction (SAED), energy-dispersive X-ray spectroscopy (EDS) and electron energy-loss spectroscopy (EELS) on the Fe L-edge. Bright-field (BF), high-angle annular dark-field (HAADF) and secondary electron (SE) imaging of nZVI acquired by a Hitachi HD-2700 STEM show near atomic resolution images and detailed morphological and structural information of nZVI. The STEM-EDS technique confirms that the fresh nZVI comprises of a metallic iron core encapsulated with a thin layer of iron oxides or oxyhydroxides. SAED patterns of the Fe core suggest the polycrystalline structure in the metallic core and amorphous nature of the oxide layer. Furthermore, Fe L-edge of EELS shows varied structural features from the innermost Fe core to the outer oxide shell. A qualitative analysis of the Fe L(2,3) edge fine structures reveals that the shell of nZVI consists of a mixed Fe(II)/Fe(III) phase close to the Fe (0) interface and a predominantly Fe(III) at the outer surface of nZVI. PMID:25050411

  14. Preparation of stabilized nano zero-valent iron particles via a rheological phase reaction method and their use in dye decolourization.

    PubMed

    Cheng, Yue; Lu, Mang; Jiao, Chuang; Liu, Hai-Jiang

    2013-01-01

    In this study, sodium carboxymethyl cellulose (NaCMC)-stabilized nano zero-valent iron (C-nZVI) was synthesized using a rheological phase reaction method. The orthogonal method was used to evaluate the factors influencing C-nZVI properties and this showed that the reaction time, solid-liquid ratio (w/v), grinding time and NaCMC concentration were all important factors. Characterization with scanning electron microscopy validated the hypothesis that the introduction of CMC led to a decrease in aggregation of iron nanoparticles. X-ray diffraction confirmed the existence of Fe(0) and the strong antioxidant activity of the iron particles. Batch decolourization experiments exhibited that solution pH, C-nZVI dosage and reaction time have significant effects on dye decolourization. A high decolourization efficiency (94.5%) was obtained within 30 min for 100 mg/L of reactive blue-19 at the optimal pH value of 5 and C-nZVI loading of 6 g/L at room temperature. The decolourization rates followed modified pseudo-first-order kinetic equations with respect to dye concentration. The observed removal rate constant was 0.0447 min(-1) for the C-nZVI loading of 6 g/L. PMID:23530358

  15. Phenol removal using zero-valent iron powder in the presence of dissolved oxygen: roles of decomposition by the Fenton reaction and adsorption/precipitation.

    PubMed

    Shimizu, Ayana; Tokumura, Masahiro; Nakajima, Koshiro; Kawase, Yoshinori

    2012-01-30

    The mechanism for removal of phenol by zero-valent iron (ZVI) was quantitatively evaluated in the presence of dissolved oxygen by varying the pH from 2 to 8.1 (natural). The measurement of OH radical concentration suggests that the removal of phenol by ZVI was occurred due to the decomposition by the Fenton reaction besides the adsorption/precipitation to the iron surface. From the measurements of dissolved organic carbon (DOC) in the filtrate with the 0.45 ?m syringe filter and the solution obtained from acidification of suspended precipitates, the roles of decomposition by the Fenton reaction and adsorption/precipitation were separately evaluated. At solution pH 3, 91% of phenol removal was achieved and 24% of TOC (total organic carbon) decreased. The contribution of the Fenton reaction was found to be 77% of overall TOC reduction. When the pH values were 4 and 5, the overall TOC removal was found to be mainly due to the adsorption/precipitation. At pH 2 and 8.1, the reduction of TOC was very small. The pH and dissolved oxygen significantly affected the dissolution of iron and the production of OH radicals and changed the roles of phenol removal by the Fenton reaction and adsorption/precipitation. PMID:22119308

  16. 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.

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

    PubMed

    Suanon, Fidle; 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 (371C) 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 604.1mgkg(-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

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

    NASA Astrophysics Data System (ADS)

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

    2010-11-01

    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, bioaccumulation, toxicity) are generally unknown. We recommend that in cases where nZVI may be chosen as the 'best' treatment option, short and long-term environmental monitoring is actively employed at these sites. We furthermore recommend the continued development of responsible nZVI innovation and better facilitated information exchange between nZVI developers, nano-risk researchers, remediation industry, and decision makers.

  19. Nanoscale zero-valent iron particles supported on reduced graphene oxides by using a plasma technique and their application for removal of heavy-metal ions.

    PubMed

    Li, Jie; Chen, Changlun; Zhang, Rui; Wang, Xiangke

    2015-06-01

    Nanoscale zero-valent iron particles supported on reduced graphene oxides (NZVI/rGOs) from spent graphene oxide (GO)-bound iron ions were developed by using a hydrogen/argon plasma reduction method to improve the reactivity and stability of NZVI. The NZVI/rGOs exhibited excellent water treatment performance with excellent removal capacities of 187.16 and 396.37?mg?g(-1) for chromium and lead, respectively. Moreover, the NZVI/rGOs could be regenerated by plasma treatment and maintained high removal ability after four cycles. X-ray photoelectron spectroscopy analysis results implied that the removal mechanisms could be attributed to adsorption/precipitation, reduction, or both. Such multiple removal mechanisms by the NZVI/rGOs were attributed to the reduction ability of the NZVI particles and the role of dispersing and stabilizing abilities of the rGOs. The results indicated that the NZVI/rGOs prepared by a hydrogen/argon plasma reduction method might be an effective composite for heavy-metal-ion removal. PMID:25917859

  20. Decomplexation and subsequent reductive removal of EDTA-chelated Cu II by zero-valent iron coupled with a weak magnetic field: Performances and mechanisms.

    PubMed

    Guan, Xiaohong; Jiang, Xiao; Qiao, Junlian; Zhou, Gongming

    2015-12-30

    The feasibility of EDTA-chelated Cu(II) (Cu(II)-EDTA) removal by zero-valent iron (Fe(0)) in the presence of a weak magnetic field (WMF) and the involved mechanisms were systematically investigated. Fe(0) combined with WMF (Fe(0)/WMF) was very effective for removing Cu(II)-EDTA at pH 4.0-6.0 with the rate constants ranging from 0.1190 min(-1) to 0.0704 min(-1). Little passivation of Fe(0) was observed during Cu(II)-EDTA removal by Fe(0)/WMF in 8 consecutive runs when 10.0 mg L(-1) Cu(II)-EDTA was dosed before the initiation of each run. The evidences presented in this study verified that Cu(II)-EDTA was removed by decomplexation followed by reduction/adsorption. In brief, Fe(II) released from Fe(0) corrosion was rapidly oxidized by oxygen to Fe(III) to chelate with EDTA and release free Cu(II), and the detached Cu(II) ions were subsequently reduced/removed by Fe(0)/Fe(II) and co-precipitated by the generated iron (hydr)-oxides. To advance the application of Fe(0)/WMF technology in real practice, a magnetic propeller agitator was designed to offer WMF inside the reactor, which could greatly improve Cu(II)-EDTA removal by Fe(0) and be easily amplified. PMID:26296073

  1. 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

  2. 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.

  3. 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

  4. Removal of As(III) and As(V) from aqueous solutions using nanoscale zero valent iron-reduced graphite oxide modified composites.

    PubMed

    Wang, Can; Luo, Hanjin; Zhang, Zilong; Wu, Yan; Zhang, Jian; Chen, Shaowei

    2014-03-15

    Nanoscale zero valent iron (NZVI) has high adsorption capacity of As(III) and As(V), but it is limited in practical use due to its small particle size and aggregation effect. Reduce graphite oxide (RGO) has been used as a support because of its high surface area. In order to utilize the advantage of NZVI and RGO as well as to avoid the disadvantage of NZVI, we loaded NZVI onto RGO via chemical reactions in this study. The adsorption capacity of As(III) and As(V), as determined from the Langmuir adsorption isotherms in batch experiments, was 35.83mgg(-1) and 29.04mgg(-1), respectively. And the adsorption kinetics fitted well with pseudo-second-order model. The residual concentration was found to meet the standard of WHO after the samples were treated with 0.4gL(-1) NZVI-RGO when the initial concentration of As(III) and As(V) were below 8ppm and 3ppm. Especially, when the initial concentration of As(III) was below 3ppm, the residual concentration was within 1ppb; whereas, the residual concentration was undetected when the initial concentration of As(III) was 1ppm. PMID:24480523

  5. 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

  6. 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

  7. Degradation pathway and kinetics of 1-alkyl-3-methylimidazolium bromides oxidation in an ultrasonic nanoscale zero-valent iron/hydrogen peroxide system.

    PubMed

    Zhou, Haimei; Shen, Yuanyuan; Lv, Ping; Wang, Jianji; Li, Pu

    2015-03-01

    Fenton and Fenton-like oxidation has been already demonstrated to be efficient for the degradation of imidazolium ionic liquids (ILs), but little is known for their degradation pathway and kinetics in such systems. In this work, degradation pathway and kinetics of 1-alkyl-3-methylimidazolium bromides ([Cnmim]Br, n=2, 4, 6, 8, and 10) were investigated in an ultrasound nanoscale zero-valent iron/hydrogen peroxide (US-nZVI/H2O2) system. For this purpose, 1-butyl-3-methylimidazolium bromide ([C4mim]Br) was used as a representative ionic liquid to optimize pH value, nZVI dose, and H2O2 concentration for the degradation reaction. Then, the degradation kinetics of [Cnmim]Br was investigated under optimal conditions, and their degradation intermediates were monitored by gas chromatography-mass spectrometry (GC-MS). It was shown that the degradation of [Cnmim]Br in such a heterogeneous Fenton-like system could be described by a second order kinetic model, and a number of intermediate products were detected. Based on these intermediate products, detailed pathways were proposed for the degradation of [Cnmim]Br in the ultrasound-assisted nZVI/H2O2 system. These findings may be useful for the better understanding of degradation mechanism of the imidazolium ILs in aqueous solutions. PMID:25463239

  8. 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, H?O? to Fe(II) molar ratio, H?O? 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

  9. [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

  10. 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

  11. 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

  12. 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

  13. Integrating classical and molecular approaches to evaluate the impact of nanosized zero-valent iron (nZVI) on soil organisms.

    PubMed

    Sacc, Maria Ludovica; Fajardo, Carmen; Costa, Gonzalo; Lobo, Carmen; Nande, Mar; Martin, Margarita

    2014-06-01

    Nanosized zero-valent iron (nZVI) is a new option for the remediation of contaminated soil and groundwater, but the effect of nZVI on soil biota is mostly unknown. In this work, nanotoxicological studies were performed in vitro and in two different standard soils to assess the effect of nZVI on autochthonous soil organisms by integrating classical and molecular analysis. Standardised ecotoxicity testing methods using Caenorhabditis elegans were applied in vitro and in soil experiments and changes in microbial biodiversity and biomarker gene expression were used to assess the responses of the microbial community to nZVI. The classical tests conducted in soil ruled out a toxic impact of nZVI on the soil nematode C. elegans in the test soils. The molecular analysis applied to soil microorganisms, however, revealed significant changes in the expression of the proposed biomarkers of exposure. These changes were related not only to the nZVI treatment but also to the soil characteristics, highlighting the importance of considering the soil matrix on a case by case basis. Furthermore, due to the temporal shift between transcriptional responses and the development of the corresponding phenotype, the molecular approach could anticipate adverse effects on environmental biota. PMID:24287264

  14. Bio-beads with immobilized anaerobic bacteria, zero-valent iron, and active carbon for the removal of trichloroethane from groundwater.

    PubMed

    Zhou, Ya-Zhen; Yang, Jie; Wang, Xiao-Li; Pan, Yue-Qing; Li, Hui; Zhou, Dong; Liu, Yong-Di; Wang, Ping; Gu, Ji-Dong; Lu, Qiang; Qiu, Yue-Feng; Lin, Kuang-Fei

    2014-10-01

    Chlorinated hydrocarbons are the most common organic pollutants in groundwater systems worldwide. In this study, we developed bio-beads with immobilized anaerobic bacteria, zero-valent iron (ZVI), and activated carbon (AC) powder and evaluated their efficacy in removing 1,1,1-trichloroethane (TCA) from groundwater. Bio-beads were produced by polyvinyl alcohol, alginate, and AC powder. We found that the concentration of AC powder used significantly affected the mechanical properties of immobilized bio-beads and that 1.0 % (w/v) was the optimal concentration. The bio-beads effectively degraded TCA (160 mg L(-1)) in the anaerobic medium and could be reused up to six times. The TCA degradation rate of bio-beads was 1.5 and 2.3 times greater, respectively, than ZVI + AC treatment or microbes + AC treatment. Measuring FeS produced by microbial reactions indicated that TCA removal occurred via FeS-catalyzed dechlorination. Analysis of clonal libraries derived from bio-beads demonstrated that the dominant species in the community were Betaproteobacteria and Gammaproteobacteria, which may contribute to the long-term stability of ZVI reactivity during TCA dechlorination. This study shows that the combined use of immobilized anaerobic bacteria, ZVI, and AC in bio-beads is effective and practical for TCA dechlorination and suggests they may be applicable towards developing a groundwater treatment system for the removal of TCA. PMID:24906831

  15. 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 factorsinitial PCMX concentration, nZVI dosage, and H2O2 concentrationwere investigated using the response surface method based on the BoxBehnken 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

  16. 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

  17. Are reproduction impairments of free spawning marine invertebrates exposed to zero-valent nano-iron associated with dissolution of nanoparticles?

    PubMed

    Kadar, Eniko; Dyson, Oliver; Handy, Richard D; Al-Subiai, Sherain N

    2013-03-01

    Studies were carried out to assess the effects of coating applied to zero-valent nano-iron (nZVI) on early life stage development of three key marine invertebrate species Mytilus galloprovincialis, Ciona intestinalis and Psammechinus milliaris. Embryo development was assessed following a 2-h exposure of the sperm to concentrations of two nZVIs of up to 10 mg l(-1) followed by in vitro fertilisation. Disruption of embryo development was most severe in sea squirts followed by mussel, while the urchin embryos were not significantly affected as compared with controls. An over twofold decrease in fertilisation success alongside significant delay in the embryo development was observed, and the effect was more severe with the coated form, possibly owing to its better colloidal stability. We provide in vitro evidence for the rapid dissolution (within 2 h) of nZVI in seawater to a degree that concentration of total solute Fe released from the coated ZVI particles exceeds safe limits of NOECs established for dissolved Fe. PMID:22263896

  18. 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.

  19. 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

  20. 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.

  1. 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

  2. A fabrication strategy for nanosized zero valent iron (nZVI)-polymeric anion exchanger composites with tunable structure for nitrate reduction.

    PubMed

    Jiang, Zhenmao; Zhang, Shujuan; Pan, Bingcai; Wang, Wenfeng; Wang, Xiaoshu; Lv, Lu; Zhang, Weiming; Zhang, Quanxing

    2012-09-30

    To reveal how the distribution of nanoscale zero-valent iron (nZVI) affect their reduction efficiency of its polymer-based composites and to further develop a simple strategy to tune the structure of the composites, we prepared four nZVI-polymerstyrene anion exchanger composites with similar nZVI loadings (13.5-14.4 Fe % in mass) but different distributions just through varying the concentration of NaBH(4) (0.9, 1.8, 3.6, and 7.2% in mass) solution during reduction of nZVI precursor (FeCl(4)(-) anions). As observed by SEM-EDX images, increasing the NaBH(4) concentration resulted in a more uniform nZVI distribution within the polymer, and thereto higher NH(4)(+)N production, faster reaction rate and more gaseous products during its reduction of nitrate and nitrite. nZVI distribution of the composites was suggested to greatly depend upon two processes, the hydrolyzation of anionic FeCl(4)(-) into cationic Fe(3+) and the reduction of both Fe(III) species by NaBH(4). Higher NaBH(4) concentration favored its faster diffusion into the inside polymer and in situ reduction of Fe(III) species into nZVI, causing a more uniform nZVI distribution. The results reported herein suggest that adjusting the NaBH(4) concentration was a simple and effective method to control the nZVI distribution in the supporting polymers, and indirectly tune the reactivity of the resultant nZVI hybrids. PMID:22795842

  3. Nanoscale zero-valent iron (nZVI) assembled on magnetic Fe3O4/graphene for chromium (VI) removal from aqueous solution.

    PubMed

    Lv, Xiaoshu; Xue, Xiaoqin; Jiang, Guangming; Wu, Donglei; Sheng, Tiantian; Zhou, Hongyi; Xu, Xinhua

    2014-03-01

    Nanoscale Zero-Valent Iron (nZVI) assembled on magnetic Fe3O4/graphene (nZVI@MG) nanocomposites was synthesized for Cr(VI) removal from aqueous solution. nZVI particles were perfectly dispersed either among Fe3O4 nanoparticles (Fe3O4 NPs) or above the basal plane of graphene. This material shows Cr(VI) removal efficiency of 83.8%, much higher than those of individuals (18.0% for nZVI, 21.6% for Fe3O4 NPs and 23.7% for graphene) and even their sum of 63.3%. The removal process obeys pseudo-second-order adsorption model, suggesting that adsorption is rate-controlling step. Maximum Cr(VI) adsorption capacity varies from 66.2 to 101.0 mg g(-1) with decreasing pH from 8.0 to 3.0 at 30°C. Negative ΔG and ΔH indicate spontaneous tendency and exothermic nature. Robust performance of nZVI@MG arises from the formation of micro-nZVI-graphene/nZVI-Fe3O4 batteries and strong adsorption capability of broad graphene sheet/Fe3O4 surfaces. Electrons released by nZVI spread all over the surfaces of graphene and Fe3O4, and the adsorbed Cr(VI) ions on them capture these floating electrons and reduce to Cr(III). Fe3O4 NPs also served as protection shell to prevent nZVI from agglomeration and passivation. PMID:24407658

  4. 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 715.16m(2)g(-1) is obtained at 900°C. nZVI with particle sizes of 20-30nm 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) (50mgL(-1)) by nZVI/OMC is near 99% within 10min 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

  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. 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...

  7. 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

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

    PubMed

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

    2012-07-25

    A new composite material based on deposition of nanosized zerovalent iron (nZVI) particles and cyanocobalamine (vitamin B12) on a diatomite matrix is presented, for catalytic transformation of organic contaminants in water. Cyanocobalamine is known to be an effective electron mediator, having strong synergistic effects with nZVI for reductive dehalogenation reactions. This composite material also improves the reducing capacity of nZVI by preventing agglomeration of iron nanoparticles, thus increasing their active surface area. The porous structure of the diatomite matrix allows high hydraulic conductivity, which favors channeling of contaminated water to the reactive surface of the composite material resulting in faster rates of remediation. The composite material rapidly degrades or transforms completely a large spectrum of water contaminants, including halogenated solvents like TCE, PCE, and cis-DCE, pesticides like alachlor, atrazine and bromacyl, and common ions like nitrate, within minutes to hours. A field experiment where contaminated groundwater containing a mixture of industrial and agricultural persistent pollutants was conducted together with a set of laboratory experiments using individual contaminant solutions to analyze chemical transformations under controlled conditions. PMID:22680618

  9. 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

  10. 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 presence of oxygen. The TCE monitoring data showed that 99% of the TCE at the site was removed by the NZVI injection. The concentrations of degradation products such as ethane and ethene increased in the monitoring wells following the NZVI injections. A lab evaluation showed that TCE degradation capacity of the injected NZVI (collected after 5 months) remained up to 30% compared with the initial capacity. Groundwater monitoring was conducted for approximately eight months to evaluate the long-term performance of the NZVI particles.

  11. [Reductive debromination of polybrominated diphenyl ethers in aquifier by nano zero-valent iron: debromination kinetics and pathway].

    PubMed

    Yang, Yu-Han; Xu, Wei-Wei; Peng, Si-Kan; Lu, Shan-Fu; Xiang, Yan; Liang, Da-Wei

    2014-03-01

    Nano-zerovalent iron (nZVI) approach is effective in the debromination of polybrominated biphenyl ethers (PBDEs). The kinetics and degradation pathway are the key issues to understand the PBDEs degradation mechanisms. In this study, nZVI, synthesized through liquid phase reduction method, coupled with Triton X-100, could completely debrominate the highly brominated congeners of a commercial octa-BDEs mixture within 46 h. The debromination of octa-BDEs could be described by means of pseudo-first-order kinetics with the reaction constant (k) of 0.106 h(-1). In case of lacking the PBDE standards, an effective approach has been developed to determine the unknown PBDE congeners using the quantitative-structure retention relationship (QSRR) model. The retention time of all 39 PBDE congeners in a standard mixture was firstly analyzed with gas chromatography coupled with an electron capture detector (GC-ECD), and the relative retention time (RRT) for each standard was obtained after normalizing the RT by the average RT of BDE47 and BDE183. Then a QSRR model was developed by fitting the RRT of each PBDE congener and its specific RRT index. The debromination products of octa-BDEs were identified using this QSRR model and the degradation pathway of octa-BDEs was elucidated. The results showed that in the stepwise reductive debromination process of PBDEs by nZVI, meta-debromin was facile to be degraded. PMID:24881384

  12. Effects of precipitation on the low-frequency electrical properties of zero valent iron: implications for monitoring PRBs

    NASA Astrophysics Data System (ADS)

    Choi, Jaeyoung; Ji, Won-Hyun; Yang, Jung-Seok; Um, Jeong-Gi; Woo, Ik; Lee, Ju-Young; Park, Young-Tae

    2010-05-01

    The relatively recent development of permeable reactive barrier (PRB) has provided a potentially viable alternative to established pump-and-treat systems for remediation of chlorinated solvent contaminated groundwater. Non-invasive methods for the assessment and monitoring of PRB have been required for evaluating long-term PRB performance and allowing effective management decisions regarding in situ site cleanup. The presence of metal in the subsurface results in the following additional charge transfer mechanisms (a) electronic conduction in the metal (b) polarization of charges at the interface between a metal and the pore-filling electrolyte. Both these mechanisms profoundly modify the measured electrical properties of the subsurface and support the utilization of electrical measurements for investigating PRB. Low frequency (0.1-1000 Hz) electrical properties are sensitive to the surface chemistry of metals in subsurface environment. In this range, electrical properties are controlled by ionic conduction through the electrolyte, surface electronic or ionic conduction, as well as diffusion mechanisms that occur at the mineral surface-pore fluid interface. Oxidation-reduction reactions may transfer electrons between mineral and fluid. The magnitude of polarization is directly related to the amount of metallic mineral surface available for charge transfer. The frequency dependence of the low frequency electrical response is indicative of the nature of electrochemical reactions occurring at the grain-fluid interface. Numerous experimental studies confirm that the frequency at which imaginary conductivity peaks inversely correlates with the grain size of the metallic particles. It is thus possible that the numerous complex surface chemical reactions involved in chlorinated solvent degradation may have distinct frequency dependent electrical signatures. In addition to the polarization term, the conduction term may also contain valuable information on PRB performance.

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

    PubMed

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

    2016-02-01

    The iron elution and dissolved oxygen (DO) consumption in organic pollutant removal by nanoscale zero-valent iron (nZVI) was examined in the range of solution pH from 3.0 to 9.0. Their behaviors were linked with the removal of organic pollutant through the dissolution of iron and the formation of iron oxide/hydroxide layer affected strongly by solution pH and DO. As an example of organic pollutants, azo-dye Orange II was chosen in this study. The chemical composition analyses before and after reaction confirmed the corrosion of nZVI into ions, the formation of iron oxide/hydroxide layer on nZVI surface and the adsorption of the pollutant and its intermediates. The complete decolorization of Orange II with nZVI was accomplished very quickly. On the other hand, the total organic carbon (TOC) removal was considerably slow and the maximum TOC removal was around 40% obtained at pH 9.0. The reductive cleavage of azo-bond by emitted electrons more readily took place as compared with the cleavage of aromatic rings of Orange II leading to the degradation to smaller molecules and subsequently the mineralization. A reaction kinetic model based on the Langmuir-Hinshelwood/Eley-Rideal approach was developed to elucidate mechanisms for organic pollutant removal controlled by the formation of iron oxide/hydroxide layer, the progress of which could be characterized by considering the dynamic concentration changes in Fe(2+) and DO. The dynamic profiles of Orange II removal linked with Fe(2+) and DO could be reasonably simulated in the range of pH from 3.0 to 9.0. PMID:26519806

  14. 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 capacity for the remediation of COPR related Cr(VI) contamination, with the synthetic nZVI demonstrating greater reactivity than the BnM. However, the biosynthesized BnM was also capable of significant Cr(VI) reduction and demonstrated a greater efficiency for the coupling of its electrons towards Cr(VI) reduction than the nZVI. PMID:26109747

  15. 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 strength, indicating their potential to improve nZVI mobility under comparable environmental conditions. In contrast, no significant change of the surface potential of brownfield sand was observed when aquifer modifiers were applied in a background solution with high ionic strength. The potential of the aquifer modifiers to promote the mobility of nZVI was furthermore tested in flow-through columns, starting with the one filled with natural quartz sand with rough surface, low ionic strength background solutions and pre-injecting lignin sulfonate in concentration of 50 mg/L. The preliminary results showed that the pre-injection of lignin sulfonate does increase mobility of nZVI under this experimental condition. Further mobility tests will be carried out in order to elucidate the potential of the aquifer modifiers to promote the mobility of nZVI in sands with a complex mineralogy and in the background solutions with varying ionic strength, in order to account for the condition that resemble those at polluted sites. This research receives funding from the European Union's Seventh Framework Programme FP7/2007-2013 under grant agreement n°309517.

  16. 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...

  17. Influence of hydrogeochemical processes on zero-valent iron reactive barrier performance: a field investigation.

    PubMed

    Liang, Liyuan; Moline, Gerilynn R; Kamolpornwijit, Wiwat; West, Olivia R

    2005-11-01

    Geochemical and mineralogical changes were evaluated at a field Fe0-PRB at the Oak Ridge Y-12 site concerning operation performance during the treatment of U in high NO3- groundwater. In the 5-yr study period, the Fe0 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-yr treatment, porosity reduction of up to 41.7% was obtained from mineralogical analysis on core samples collected at the upgradient gravel-Fe0 interface. Elsewhere, Fe0 filings were loose with some cementation. Fe0 corrosion and pore volume reduction at this site are more severe due to the presence of NO3- 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 Fe0 and transported outside the PRB. Based on the equilibrium reductions of NO3- and SO4(2-) by Fe0 and mineral precipitation, geochemical modeling predicted a maximum of 49% porosity loss for 5 yr 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. PMID:16126304

  18. Influence of hydrogeochemical processes on zero-valent iron reactive barrier performance: a field investigation.

    PubMed

    Liang, Liyuan; Moline, Gerilynn R; Kamolpornwijit, Wiwat; West, Olivia R

    2005-08-01

    Geochemical and mineralogical changes were evaluated at a field Fe0-PRB at the Oak Ridge Y-12 site concerning operation performance during the treatment of U in high NO3- groundwater. In the 5-year study period, the Fe0 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-Fe0 interface. Elsewhere, Fe0 filings were loose with some cementation. Fe0 corrosion and pore volume reduction at this site are more severe due to the presence of NO3- 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 Fe0 and transported outside the PRB. Based on the equilibrium reductions of NO3- and SO4(2-) by Fe0 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. PMID:16051393

  19. 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.'

  20. 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.

  1. A two and half-year-performance evaluation of a field test on treatment of source zone tetrachloroethene and its chlorinated daughter products using emulsified zero valent iron nanoparticles.

    PubMed

    Su, Chunming; Puls, Robert W; Krug, Thomas A; Watling, Mark T; O'Hara, Suzanne K; Quinn, Jacqueline W; Ruiz, Nancy E

    2012-10-15

    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) and its chlorinated daughter products. Two EZVI delivery methods were used: pneumatic injection and direct injection. In the pneumatic injection plot, 2180 L of EZVI containing 225 kg of iron (Toda RNIP-10DS), 856 kg of corn oil, and 22.5 kg of surfactant were injected to remedy an estimated 38 kg of CVOCs. In the direct injection plot, 572 L of EZVI were injected to treat an estimated 0.155 kg of CVOCs. After injection of the EZVI, significant reductions in PCE and trichloroethene (TCE) concentrations were observed in downgradient wells with corresponding increases in degradation products including significant increases in ethene. In the pneumatic injection plot, there were significant reductions in the downgradient groundwater mass flux values for PCE (>85%) and TCE (>85%) and a significant increase in the mass flux of ethene. There were significant reductions in total CVOC mass (86%); an estimated reduction of 63% in the sorbed and dissolved phases and 93% reduction in the PCE DNAPL mass. There are uncertainties in these estimates because DNAPL may have been mobilized during and after injection. Following injection, significant increases in dissolved sulfide, volatile fatty acids (VFA), and total organic carbon (TOC) were observed. In contrast, dissolved sulfate and pH decreased in many wells. The apparent effective remediation seems to have been accomplished by direct abiotic dechlorination by nanoiron followed by biological reductive dechlorination stimulated by the corn oil in the emulsion. PMID:22868086

  2. 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...

  3. 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.

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

    PubMed

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

    2014-12-01

    The role of Fe(II) and Fe(III) in U(VI) reduction by nanoscale zerovalent iron (nanoFe0) was investigated using two iron chelators 1,10-phenanthroline and triethanolamine (TEA) under a CO2-free anoxic condition. The results showed that U(VI) reduction was strongly inhibited by 1,10-phenanthroline and TEA in a pH range from 6.9 to 9.0. For instance, at pH 6.9 the observed U(VI) reduction rates decreased by 81% and 82% in the presence of 1,10-phenanthroline and TEA, respectively. The inhibition was attributed to the formation of stable complexes between 1,10-phenanthroline and Fe(II) or TEA and Fe(III). In the absence of iron chelators, U(VI) reduction can be enhanced by surface-bound Fe(II) on nanoFe0. Our results suggested that Fe(III) and Fe(II) possibly acted as an electron shuttle to ferry the electrons from nanoFe0 to U(VI), therefore a combined system with Fe(II), Fe(III) and nanoFe0 could facilitate U(VI) reductive immobilization in the contaminated groundwater. PMID:25461927

  5. 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

  6. Effect of kaolinite, silica fines and pH on transport of polymer-modified zero valent iron nano-particles in heterogeneous porous media.

    PubMed

    Kim, Hye-Jin; Phenrat, Tanapon; Tilton, Robert D; Lowry, Gregory V

    2012-03-15

    Polymer coatings on nano-sized remediation agents and subsurface heterogeneity will affect their transport, likely in a pH-dependent manner. The effect of pH on the aggregation of polymer-coated nanoscale zerovalent iron (nZVI) and its deposition onto sand and clay (kaolinite) surfaces was studied. nZVI coatings included a high molecular weight (90 kg/mol) strong polyanion, poly(methacrylic acid)-b-(methy methacrylate)-b-(styrenesulfonate) (PMAA-PMMA-PSS) and a low molecular weight (2.5 kg/mol) weak polyanion, polyaspartate. Aggregation and deposition increased with decreasing pH for both polyelectrolytes. The extent was greater for the low MW polyaspartate coated nZVI. Enhanced deposition at lower pH was indicated because the elutability of polyaspartate-modified hematite (which did not aggregate) also decreased at lower pH. The greater deposition onto clay minerals compared to similar sized silica fines is attributed to charge heterogeneity on clay mineral surfaces, which is sensitive to pH. Heteroaggregation between kaolinite particles and nZVI over the pH range 6-8 confirmed this assertion. Excess unadsorbed polyelectrolyte in solution (100mg/L) enhanced the transport of modified nZVI by minimizing aggregation and deposition onto sand and clay. These results indicate that site physical and chemical heterogeneity must be considered when designing an nZVI emplacement strategy. PMID:22284571

  7. 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 90C 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.

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

    PubMed

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

    2014-07-15

    In this study, the synthesis and characterization of a new adsorbent containing nanoscale zerovalent iron particles (NZVI) decorated sineguelas waste (S-NaOH-NZVI) from agriculture biomass was investigated for the adsorption/reduction of inorganic pollution such as Pb(II) ions. The combination of ZVI particles on the surface of sineguelas waste can help to overcome the disadvantage of ultra-fine powders which may have strong tendency to agglomerate into larger particles, resulting in an adverse effect on both effective surface area and catalyst performance. The synthesized materials were characterized with different methods such as FT-IR, BET, XRD, TEM and pHPZC. Good dispersion of NZVI particles (ca. 10-70nm) on the sineguelas waste was observed. The effects of various parameters, such as contact time, pH, concentration, adsorbent dosage and temperature were studied. The adsorption of Pb(II) ions has been studied in terms of pseudo-first- and second-order kinetics, and the Freundlich, Langmuir and Langmuir-Freundlich isotherms models have also been used to the equilibrium adsorption data. The adsorption kinetics followed the mechanism of the pseudo-second-order equation. The thermodynamic parameters (?G, ?H and ?S) indicated that the adsorption of Pb(II) ions were feasible, spontaneous and endothermic at 25-80C. XRD analysis indicated the presence of Pb(0) on the S-NaOH-NZVI surface. This study suggests that the modified sineguelas waste by NZVI particles can be prepared at low cost and the materials are environmentally benign for the removal of Pb(II) ions, and likely many other heavy metal ions, from water. PMID:24863789

  9. DIRECT PUSH METHODS FOR LOCATING AND COLLECTING CORES OF AQUIFER SEDIMENT AND ZERO-VALENT IRON FROM PERMEABLE REACYTIVE BARRIERS

    EPA Science Inventory

    It is often necessary to collect core samples that do not fit the normal sampling protocol. This Field Innovation Forum submission describes new methodology that enables researchers to collect soil samples in situations where the normal vertical sampling techniques will deliver ...

  10. 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...

  11. 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.

  12. Zero-valent aluminum for oxidative degradation of aqueous organic pollutants.

    PubMed

    Bokare, Alok D; Choi, Wonyong

    2009-09-15

    Oxidative degradation of aquatic organic contaminants using zero-valent aluminum (ZVAl) in the presence of dissolved oxygen (O2) was investigated. The metal corrosion process in acidic conditions (pH < 4) was accompanied by electron transfer from ZVAl to O2, which led to the simultaneous generation of Al3+ and hydrogen peroxide (H2O2). The oxidation of 4-chlorophenol (4-CP), a model substrate, was initiated by the generation of hydroxyl radicals (HO*) via electron transfer from Al0 to H2O2. Degradation was initiated after an induction period of about 2 h, during which the native oxide layer was dissoluted. The HO*(-) mediated oxidation reaction was completely quenched by adding methanol as a radical scavenger. Systematic studies on the effects of ZVAl loading, pH, and surface oxide content revealed that the oxide layer dissolution controlled the Al0-mediated oxidation of 4-CP. The proposed process is similarly compared with the zero-valent iron (ZVI) system, but the ZVAl/O2 system showed a higher oxidation capacity compared with ZVI/O2 because of the stability of aquo-complexed Al3+ ions over a wider pH range. The degradation of phenol, nitrobenzene, and dichloroacetate was also successfully achieved with ZVAl. The present study proposes the ZVAl/O2 process as a viable method of oxidative water treatment. PMID:19806753

  13. 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...

  14. 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...

  15. AMELIORATION OF ACID MINE DRAINAGE USING REACTIVE MIXTURES IN PERMEABLE REACTIVE BARRIERS

    EPA Science Inventory

    The generation and release of acidic drainage from mine wastes is an environmental problem of international scale. The use of zero-valent iron and/or iron mixtures in subsurface Permeable Reactive Barriers (PRB) presents a possible passive alternative for remediating acidic grou...

  16. 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 physical and chemical understanding that is necessary for the development of cleanup techniques and procedures.

  17. The remediation performance of a specific electrokinetics integrated with zero-valent metals for perchloroethylene contaminated soils.

    PubMed

    Chang, Jih-Hsing; Cheng, Shu-Fen

    2006-04-17

    This research was conducted to evaluate an integrated technique, combination of the electrokinetics (EK) and zero-valent metal (ZVM), for remediation of the perchloroethylene (PCE) contaminated soils. Various experimental conditions were controlled such as different voltage gradients, the position of ZVM, and ZVM species. The appropriate operational parameters are concluded as follows: (1) 0.01 M sodium carbonate serves as the working solution; (2) the voltage gradient is controlled at 1.0 V/cm; (3) ZVM wall is settled close to the anode. Based on the above operation conditions, the pH value of working solution can maintain at neutral range for avoiding the soil acidification. Neutral pH also causes the system to stay at a stable status of electricity consumption. The removal efficiency reaches 99% and 90% for decontaminating the PCE in the pore-water and the soil, respectively, after a 10-day treatment. The zero-valent zinc performs better PCE degradation than zero-valent iron. Moreover, the soils treated by EK+ZVM still possess their original properties. PMID:16214288

  18. 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.

  19. 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. ...

  20. Applications of zero-valent silicon nanostructures in biomedicine.

    PubMed

    Kafshgari, Morteza Hasanzadeh; Voelcker, Nicolas H; Harding, Frances J

    2015-08-01

    Zero-valent, or elemental, silicon nanostructures exhibit a number of properties that render them attractive for applications in nanomedicine. These materials hold significant promise for improving existing diagnostic and therapeutic techniques. This review summarizes some of the essential aspects of the fabrication techniques used to generate these fascinating nanostructures, comparing their material properties and suitability for biomedical applications. We examine the literature in regards to toxicity, biocompatibility and biodistribution of silicon nanoparticles, nanowires and nanotubes, with an emphasis on surface modification and its influence on cell adhesion and endocytosis. In the final part of this review, our attention is focused on current applications of the fabricated silicon nanostructures in nanomedicine, specifically examining drug and gene delivery, bioimaging and biosensing. PMID:26295171

  1. 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.

  2. ACCUMULATION RATE OF MICROBIAL BIOMASS AT TWO PERMEABLE REACTIVE BARRIER SITES

    EPA Science Inventory

    Accumulation of mineral precipitates and microbial biomass are key factors that impact the long-term performance of in-situ Permeable Reactive Barriers for treating contaminated groundwater. Both processes can impact remedial performance by decreasing zero-valent iron reactivity...

  3. 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...

  4. PERMEABLE REACTIVE SUBSURFACE BARRIERS FOR THE INTERCEPTION AND REMEDIATION OF CHLORINATED HYDROCARBON AND CHROMIUM (VI) PLUMES IN GROUND WATER

    EPA Science Inventory

    This document concerns the use of permeable reactive subsurface barriers for the remediation of plumes of chlorinated hydrocarbons and Cr(VI) species in ground water, using zero-valent iron (Fe0) as the reactive substrate. Such systems have undergone thorough laboratory research,...

  5. TREATMENT OF METALS IN GROUND WATER USING AN ORGANIC-BASED SULFATE-REDUCING PERMEABLE REACTIVE BARRIER

    EPA Science Inventory

    A pilot permeable reactive barrier (PRB) consisting of a mixture of leaf compost, zero-valent iron (ZVI) filings, limestone and pea gravel was evaluated at a former phosphate fertilizer manufacturing facility in Charleston, S.C. The PRB is designed to treat arsenic and heavy met...

  6. Remediation of Perchloroethylene Contaminated Groundwater by Permeable Reactive Barrier Using Iron, Granular Activated Carbon, and Soil

    NASA Astrophysics Data System (ADS)

    Jeon, L.; Lee, D.; Chang, H.

    2005-12-01

    The objective of this study is to evaluate the effects of zero-valent iron (ZVI), granular activated carbon (GAC) and soil as materials to build permeable reactive barrier (PRB). Flow-through Column experiments were conducted to evaluate the reactivity and adsorptive capacity of various materials for Perchloroethylene(PCE) contaminated groundwater. Columns were packed with various materials such as ZVI, GAC, and Soil. A peristaltic pump was used to feed this medium at 2.5mL/h resulting in a hydraulic retention time of approximately 70h. The column which packed only the soil shows PCE contamination came out passing after 10 pore volumes. But the other columns are continued purification effect.

  7. Catalytic transformation of persistent contaminants using a new composite material based on nanosized zero-valent metal - field experiment results

    NASA Astrophysics Data System (ADS)

    Dror, I.; Merom Jacov, O.; Berkowitz, B.

    2010-12-01

    A new composite material based on deposition of nanosized zero valent iron (ZVI) particles and cyanocobalamine (vitamin B12) on a diatomite matrix is presented. Cyanocobalamine is known to be an effective electron mediator, having strong synergistic effects with ZVI for reductive dehalogenation reactions. This composite material also improves the reducing capacity of nanosized ZVI by preventing agglomeration of iron particles, thus increasing their active surface area. The porous structure of the diatomite matrix allows high hydraulic conductivity, which favors channeling of contaminated water to the reactive surface of the composite material and in turn faster rates of remediation. The ability of the material to degrade or transform rapidly and completely a large spectrum of water pollutants will be demonstrated, based on results from two field site experiments where polluted groundwater containing a mixture of industrial and agricultural persistent pollutants was treated. In addition a set of laboratory experiments using individual contaminant solutions to analyze chemical transformations under controlled conditions will be presented.

  8. 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.

  9. 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.

  10. Performance Evaluation of In-Situ Iron Reactive Barriers at the Oak Ridge Y-12 Site

    SciTech Connect

    Watson, D.B.

    2003-12-30

    In November 1997, a permeable iron reactive barrier trench was installed at the S-3 Ponds Pathway 2 Site located at the Y-12 Plant, Oak Ridge, Tennessee. The overall goal of the project is to evaluate the ability of permeable reactive barrier technology to remove uranium, nitrate, and other inorganic contaminants in groundwater and to assess impacts of biogeochemical interactions on long-term performance of the treatment system. Zero-valent iron (Fe0) was used as the reactive medium, which creates a localized zone of reduction or low oxidation reduction potential (ORP), elevated pH, and dissolved H{sub 2} as Fe{sup 0} corrodes in groundwater. These conditions favor the removal of metals and radionuclides (such as uranium and technetium) through redox-driven precipitation and/or sorption to iron corrosion byproducts, such as iron oxyhydroxides. The technology is anticipated to be economical and low in maintenance as compared with conventional pump-and-treat technology. Groundwater monitoring results indicate that the iron barrier is effectively removing uranium and technetium, the primary contaminants of concern, as anticipated from our previous laboratory studies. In addition to uranium and technetium, nitrate, sulfate, bicarbonate, calcium, and magnesium are also found to be removed, either partially or completely by the iron barrier. Elevated concentrations of ferrous ions and sulfide, and pH were observed within the iron barrier. Although ferrous iron concentrations were initially very high after barrier installation, ferrous ion concentrations have decreased to low to non-detectable levels as the pH within the iron has increased over time (as high as 9 or 10). Iron and soil core samples were taken in February 1999 and May 2000 in order to evaluate the iron surface passivation, morphology, mineral precipitation and cementation, and microbial activity within and in the vicinity of the iron barrier. Results indicate that most of the iron filings collected in cores were still loose and not clogged after approximately 2.5 years of barrier installation. However, significant amounts of cemented iron filings were observed in the upgradient portion of the iron. In particular, the cementation appeared to have increased significantly over time from the 1999 to 2000 coring events in both the upgradient and downgradient portions of the iron. Minerals identified by scanning electron microscope (SEM), energy dispersive x-ray (EDX), and x-ray diffraction (XRD) that have precipitated in the iron include iron sulfide, calcium carbonate (aragonite), iron oxyhydroxides (goethite, akagneite, amorphous), siderite (iron carbonate), makinawite, and green rusts. These mineral precipitants are responsible for the cementation observed within the iron barrier. Elevated microbial activity and increased diversity within and in the vicinity of the iron barrier were also observed, particularly denitrifiers and sulfate-reducers, which may have been responsible or partially responsible for the removal of nitrate and sulfate in groundwater and the formation of ferrous sulfide minerals within the iron barrier. Hydraulic gradients across the Pathway 2 site have remained relatively stable and consistent from east to west. Increases and decreases in the gradients across the site observed over the past 2.5 years appear to be primarily related to recharge during precipitation events and seasonal fluctuations. However, closer inspection of gradient fluctuations within the iron appear to indicate that cementation within the iron may be starting to impact groundwater flow through the iron. Since the spring of 1999, recharge events have had a more pronounced impact on hydraulic gradients observed between wells located upgradient, within, and downgradient of the iron. This data suggests that the connectivity of the iron and gravel in the upgradient portion of the trench to the iron and gravel in the downgradient portion of the trench may be decreasing over time due to cementation in the iron.

  11. 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 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 the fundamental physical and chemical understanding that is necessary for the development of cleanup techniques and procedures. As of May 1998, they have performed both bulk chemical measurements of the reduction reactions and surface science studies of model chemical systems. During these first two years of funding, the authors have made significant progress in both areas. Initially, they focused primarily on the reduction of selenate by elemental iron. They also performed some work with chromate, perchlorate, uranyl, and carbon tetrachloride. In the following sections some of the progress is described.'

  12. 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 with initial bacterial inoculation and organic substrate dosing, in order to predict the effects of bacterial overgrowth and gas generation. During construction particular care should be taken in order to minimize the amount of used biopolymer so that complete breakdown can be achieved. PMID:19329678

  13. Synthesis of zero-valent copper-chitosan nanocomposites and their application for treatment of hexavalent chromium.

    PubMed

    Wu, Shao-Jung; Liou, Tzong-Horng; Mi, Fwu-Long

    2009-10-01

    This study used ionotropic crosslinking to synthesize chitosan-tripolyphosphate chelating resin beads, which are used to fabricate zero-valent copper-chitosan nanocomposites. The copper nanoparticles were dispersed on chitosan-tripolyphosphate beads, and were thus able to maintain appropriate dispersion and stability, which greatly improves their applicability. The fabrication process contains two steps: using chitosan-tripolyphosphate beads to adsorb Cu(II) ions, followed by chemical reduction to reduce Cu(II) ions to zero-valent copper. This study explored the adsorption of synthesized chitosan-tripolyphosphate beads to Cu(II) ions, and used SEM/EDS, XPS, and TEM to examine the properties of zero-valent copper-chitosan nanocomposites. The results showed that, the adsorption behavior of hexavalent chromium from aqueous solution onto fabricated nanocomposites has better adsorption capacity than that of the chitosan-tripolyphosphate beads. PMID:19414251

  14. Enhanced decolorization of methyl orange using zero-valent copper nanoparticles under assistance of hydrodynamic cavitation.

    PubMed

    Li, Pan; Song, Yuan; Wang, Shuai; Tao, Zheng; Yu, Shuili; Liu, Yanan

    2015-01-01

    The rate of reduction reactions of zero-valent metal nanoparticles is restricted by their agglomeration. Hydrodynamic cavitation was used to overcome the disadvantage in this study. Experiments for decolorization of methyl orange azo dye by zero-valent copper nanoparticles were carried out in aqueous solution with and without hydrodynamic cavitation. The results showed that hydrodynamic cavitation greatly accelerated the decolorization rate of methyl orange. The size of nanoparticles was decreased after hydrodynamic cavitation treatment. The effects of important operating parameters such as discharge pressure, initial solution pH, and copper nanoparticle concentration on the degradation rates were studied. It was observed that there was an optimum discharge pressure to get best decolorization performance. Lower solution pH were favorable for the decolorization. The pseudo-first-order kinetic constant for the degradation of methyl orange increased linearly with the copper dose. UV-vis spectroscopic and Fourier transform infrared (FT-IR) analyses confirmed that many degradation intermediates were formed. The results indicated hydroxyl radicals played a key role in the decolorization process. Therefore, the enhancement of decolorization by hydrodynamic cavitation could due to the deagglomeration of nanoparticles as well as the oxidation by the in situ generated hydroxyl radicals. These findings greatly increase the potential of the Cu(0)/hydrodynamic cavitation technique for use in the field of treatment of wastewater containing hazardous materials. PMID:24948487

  15. 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

  16. EPA/ITRC-RTDF permeable reactive barrier short course. Permeable reactive barriers: Application and deployment

    SciTech Connect

    1999-11-01

    This report focuses on the following: Permeable Reactive Barriers: Application and Deployment; Introduction to Permeable Reactive Barriers (PRBs) for Remediating and Managing Contaminated Groundwater in Situ; Collection and Interpretation of Design Data 1: Site Characterization for PRBs; Reactive Materials: Zero-Valent Iron; Collection and Interpretation of Design Data 2: Laboratory and Pilot Scale Tests; Design Calculations; Compliance Monitoring, Performance Monitoring and Long-Term Maintenance for PRBs; PRB Emplacement Techniques; PRB Permitting and Implementation; Treatment of Metals; Non-Metallic Reactive Materials; Economic Considerations for PRB Deployment; and Bibliography.

  17. EPA/ITRC-RTDF permeable reactive barrier short course. Permeable reactive barriers: Application and deployment

    SciTech Connect

    Not Available

    1999-01-01

    This report focuses on the following: Permeable Reactive Barriers: Application and Deployment; Introduction to Permeable Reactive Barriers (PRBs) for Remediating and Managing Contaminated Groundwater in Situ; Collection and Interpretation of Design Data 1: Site Characterization for PRBs; Reactive Materials: Zero-Valent Iron; Collection and Interpretation of Design Data 2: Laboratory and Pilot Scale Tests; Design Calculations; Compliance Monitoring, Performance Monitoring and Long-Term Maintenance for PRBs; PRB Emplacement Techniques; PRB Permitting and Implementation; Treatment of Metals; Non-Metallic Reactive Materials; Economic Considerations for PRB Deployment; and Bibliography.

  18. 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 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 investigations of the interactions of the relevant chlorinated solvents, trace elements, and trace element-containing compounds with single- and poly-crystalline Fe 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. The authors are perforrming both bulk chemical measurements of the reduction reactions and surface science studies of model chemical systems. During this first year of funding, the authors have already made significant progress in both areas. Initially, they have focused primarily on the reduction of selenate by elemental iron. They have also performed some work with chromate, perchlorate, uranyl, and carbon tetrachloride, as well. In the following sections, some of the progress is described.'

  19. The use of carbon fiber composites as substrate for a zero valent metal dechlorination system

    SciTech Connect

    Andrews, R.; Spears, B.; Grulke, E.

    1996-12-31

    The use of zero valent metals is known to successfully degrade chlorinated hydrocarbons. The use of zinc metal to dechlorinate trichloroethane (TCE) in contaminated groundwater sources has been limited by metal surface area for reaction. A highly porous carbon fiber composite substrate for the zinc metal provides a much higher surface area for reaction in a dechlorination system. The zinc coating applied to the carbonaceous fibers provides higher reaction rates than traditional powdered metal systems. Added advantages of using the zinc coated carbon substrate for ground water clean up are low pressure drop, easy removal and emplacement of composites, and the ability to recharge the zinc coating in situ. The novel zinc impregnation method results in a uniform coating of zinc throughout the composite and a greatly increased area for reaction.

  20. Low-Frequency Electrical Properties of Zero Vvalent Iron-Sand Columns: Implications for Monitoring the Performance of Reactive Iron Wall Barriers

    NASA Astrophysics Data System (ADS)

    Choi, J.; Slater, L. D.; Wu, Y.

    2003-12-01

    The reactive iron barrier is an in-situ technology for passive remediation of chlorinated solvents and heavy metals. Redox reactions occurring on the iron surface effectively remove these contaminants from groundwater. The effectiveness of this redox reaction diminishes with time due to oxidation and precipitation occurring on the metal surface, such that the long-term performance of reactive barriers is uncertain. Non-invasive measurement methods for evaluating reactive barrier performance are thus required to support remedial strategies at reactive barrier installations. Low-frequency (0.1-1000 Hz) electrical measurements are sensitive to the electrochemistry of the metal surface-pore fluid interface. We are conducting a series of laboratory experiments to assess the sensitivity of electrical methods (induced polarization and resistivity) to changes in the physicochemical properties of the metal-fluid interface that occur over time. In this paper we present the results of baseline studies on zero-valent iron-sand columns as a function of (a) reactive iron concentration (b) saturating fluid chemistry, and (c) degree of surface oxidation. The sensitivity of low-frequency electrical parameters to total zero-valent iron (Fe0) surface area was investigated by synthesizing Fe-Ottawa sand samples with varying Fe0 concentration from 0-10 percent. The dependence on ionic strength and electrolyte activity was investigated by making measurements on samples saturated with 0.001-1.0 for NaNO3, NaCl and CaCl2 solutions. The effect of pH was evaluated at constant electrolyte activity. As a first step towards evaluating the sensitivity of electrical measurements to reduction in reactive iron performance, measurements were made over a three month period of ageing and correlated with geochemical indicators (pH, Eh, electrical conductivity, iron concentrations) of Fe surface oxidation and precipitation. We find that induced polarization (IP) parameters are highly sensitive to Fe0 surface area whereas conduction parameters measured with the resistivity method are insensitive to Fe0 concentration over the investigated range. Polarization at the iron-electrolyte interface shows a power law relationship with electrolyte activity for all solutions and is consistent with Warburg impedance theory. Power-law exponents are slightly higher than that predicted for the active ion species based on Warburg impedance theory. Polarization magnitude depends on ionic composition of the electrolyte with the magnitude following the order CaCl2: NaCl: NaNO3. Conduction parameters are insensitive to ionic composition at constant electrolyte activity. Electrolyte activity exerts a strong control on the polarization relaxation length-scale, with time constant of the relaxation decreasing with increasing electrolyte activity. Polarization parameters measured during three months of ageing are clearly correlated with time and suggest that electrical measurements are sensitive to reduction in reactive iron performance.

  1. 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.

  2. 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.

  3. Stabilization of engineered zero-valent nanoiron with Na-acrylic copolymer enhances spermiotoxicity.

    PubMed

    Kadar, Eniko; Tarran, Glenn A; Jha, Awadhesh N; Al-Subiai, Sherain N

    2011-04-15

    Studies were carried out to assess the effects of stabilized (i.e., coated with organic polyacrylic stabilizer) and nonstabilized forms of zero-valent nanoiron (nZVI) on the development of Mytilus galloprovincialis embryos following 2 h exposure of the sperm prior to in vitro fertilization. Both forms of nZVI caused serious disruption of development, consisting of 30% mortality among spermatozoa with subsequent 20% decline in fertilization success, and delay in development, i.e., over 50% of the larvae were suspended in the trochophore stage. Significant DNA damage was also detected in sperm exposed to the highest exposure concentrations (10 mg L(-1)). Distinct dose response to the two different types of nZVI observed are linked to aggregation behavior that is controlled by the surface stabilizers. This work reports on conventional biomarkers (for membrane integrity, genotoxicity, and developmental toxicity) applied for the rapid assessment of toxicity of nZVI, which are able to detect surface property-related effects to meet the requirements of risk assessments for nanotechnology. The study highlights the potential ecotoxicological impact of an environmentally relevant engineered nanoparticle. Implications of the NOM-nZVI interactions regarding soil and groundwater remediation and wastewater treatment are discussed. PMID:21291273

  4. 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.

  5. 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.

  6. 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

  7. 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...

  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. Changes in Ground-Water Quality near Two Granular-Iron Permeable Reactive Barriers in a Sand and Gravel Aquifer, Cape Cod, Massachusetts, 1997-2000

    USGS Publications Warehouse

    Savoie, Jennifer G.; Kent, Douglas B.; Smith, Richard L.; LeBlanc, Denis R.; Hubble, David W.

    2004-01-01

    Two experimental permeable reactive barriers (PRBs) of granular zero-valent iron were emplaced in the path of a tetrachloroethene plume (the Chemical Spill-10 plume) at the Massachusetts Military Reservation, Cape Cod, Massachusetts, in June 1998. The goal of the field experiment was to achieve emplacement of a granular-iron PRB deeper than attempted before. The PRBs were expected to create a reducing environment and degrade the tetrachloroethene by reductive dechlorination. The goal of the work presented in this report was to observe temporary and sustained changes to the ground-water chemistry downgradient from the PRBs. A hydraulic-fracturing method involving injection of the granular iron with a guar-biopolymer and enzyme slurry was used to install the parallel 30- to 33-foot-wide wall-shaped barriers at a depth of 82 to 113 feet below land surface. An acetic acid and enzyme mixture was subsequently injected in wells near the barriers to degrade the guar biopolymer. Prior to the emplacement, tetrachloroethene concentrations in the Chemical Spill-10 plume at the study area were as high as 250 micrograms per liter. Other water properties in the plume generally were similar to the properties of uncontaminated ground water in the area, which typically has dissolved oxygen concentrations of 250 to 375 micromoles per liter, pH of 5.5 to 6.0, and specific conductance of 60 to 90 microsiemens per centimeter. Water-quality samples were collected periodically from monitoring wells near the PRBs to determine how the emplacement of the granular-iron walls altered the ground-water quality. In addition, an automated well-sampling device measured temperature, specific conductance, pH, and dissolved oxygen every 1?4 days for 16 months in a well downgradient from the two parallel PRBs. Temporary increases (lasting about 5 to 6 months) in specific conductance were observed downgradient from the PRBs as a result of the sodium chloride, potassium carbonate, and other salts included in the slurry and the acetic acid and enzyme mixture that was subsequently injected to degrade the guar biopolymer. Temporary increases in the concentrations of major cations (sodium, potassium, magnesium, and calcium) were observed downgradient from the PRBs, as were temporary but substantial increases in the dissolved and total organic carbon concentrations. Methane was detected, sulfate concentrations decreased temporarily, and concentrations of dissolved inorganic carbon increased in samples from wells downgradient from the PRBs. A sustained (longer than 12 months) reducing environment, in which dissolved oxygen concentrations decreased to zero, the pH increased to about 6.8, and dissolved iron concentrations increased substantially, developed as a result of the oxidation (corrosion) of the granular iron; this zone persisted at least 65 feet downgradient from the PRBs. The pH and dissolved iron concentrations increased with distance from the granular-iron walls. Concentrations of arsenic, cobalt, manganese, and phosphorus increased, and nitrate concentrations were reduced to below the detection limit downgradient from the walls. A sustained decrease of tetrachloroethene concentrations was not observed; however, reductive dechlorination products were observed at wells downgradient from the PRBs during several rounds of sampling. The emplacement of zero-valent iron in the aquifer to remove tetrachloroethene from the ground water caused changes in the water chemistry that persisted farther downgradient from the PRBs than has been observed at other sites because of the low chemical reactivity of the quartz-dominated aquifer sediments and the low ambient dissolved chemical concentrations in the ground water. The small transverse dispersion in the aquifer and the probable long-term persistence of the iron indicate that the chemically altered zone probably will extend a substantial distance downgradient from the PRBs for a substantial period of time (years); fur

  10. Ultrasound-assisted activation of zero-valent magnesium for nitrate denitrification: identification of reaction by-products and pathways.

    PubMed

    Ileri, Burcu; Ayyildiz, Onder; Apaydin, Omer

    2015-07-15

    Zero-valent magnesium (Mg(0)) was activated by ultrasound (US) in an aim to promote its potential use in water treatment without pH control. In this context, nitrate reduction was studied at batch conditions using various doses of magnesium powder and ultrasound power. While neither ultrasound nor zero-valent magnesium alone was effective for reducing nitrate in water, their combination removed up to 90% of 50 mg/L NO3-N within 60 min. The rate of nitrate reduction by US/Mg(0) enhanced with increasing ultrasonic power and magnesium dose. Nitrogen gas (N2) and nitrite (NO2(-)) were detected as the major reduction by-products, while magnesium hydroxide Mg(OH)2 and hydroxide ions (OH(-)) were identified as the main oxidation products. The results from SEM-EDS measurements revealed that the surface oxide level decreased significantly when the samples of Mg(0) particles were exposed to ultrasonic treatment. The surface passivation of magnesium particles was successfully minimized by mechanical forces of ultrasound, which in turn paved the way to sustain the catalyst activity toward nitrate reduction. PMID:25781370

  11. BIFUNCTIONAL ALUMINUN: A PERMEABLE BARRIER MATERIAL FOR THE DEGRADATION OF MTBE

    EPA Science Inventory

    Bifunctional aluminum is an innovative remedial material for the treatment of gasoline oxygenates in permeable reactive barriers (PRBs). PRBs represent a promising environmental technology for remediation of groundwater contamination. Although zero-valent metals (ZVM) have been...

  12. 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 iron.

  13. 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.

  14. 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...

  15. 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...

  16. 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...

  17. Enhanced ozonation degradation of di-n-butyl phthalate by zero-valent zinc in aqueous solution: performance and mechanism.

    PubMed

    Wen, Gang; Wang, Sheng-Jun; Ma, Jun; Huang, Ting-Lin; Liu, Zheng-Qian; Zhao, Lei; Su, Jun-Feng

    2014-01-30

    Enhanced ozonation degradation of di-n-butyl phthalate (DBP) by zero-valent zinc (ZVZ) has been investigated using a semi-continuous reactor in aqueous solution. The results indicated that the combination of ozone (O3) and ZVZ showed an obvious synergetic effect, i.e. an improvement of 54.8% on DBP degradation was obtained by the O3/ZVZ process after 10min reaction compared to the cumulative effect of O3 alone and O2/ZVZ. The degradation efficiency of DBP increased gradually with the increase of ZVZ dosage, enhanced as solution pH increasing from 2.0 to 10.0, and more amount of DBP was degraded with the initial concentration of DBP arising from 0.5 to 2.0mgL(-1). Recycling use of ZVZ resulted in the enhancement of DBP degradation, because the newly formed zinc oxide took part in the reaction. The mechanism investigation demonstrated that the enhancement effect was attributed to the introduction of ZVZ, which could promote the utilization of O3, enhance the formation of superoxide radical by reducing O2 via one-electron transfer, accelerate the production of hydrogen peroxide and the generation of hydroxyl radical. Additionally, the newly formed zinc oxide on ZVZ surface also contributed to the enhancement of DBP degradation in the recycling use of ZVZ. Most importantly, the O3/ZVZ process was also effective in enhanced ozonation degradation of DBP under the background of actual waters. PMID:24333716

  18. Assessment of solid reactive mixtures for the development of biological permeable reactive barriers.

    PubMed

    Pagnanelli, Francesca; Viggi, Carolina Cruz; Mainelli, Sara; Toro, Luigi

    2009-10-30

    Solid reactive mixtures were tested as filling material for the development of biological permeable reactive barriers for the treatment of heavy metals contaminated waters. Mixture selection was performed by taking into account the different mechanisms operating in sulphate and cadmium removal with particular attention to bioprecipitation and sorption onto the organic matrices in the mixtures. Suspensions of eight reactive mixtures were tested for sulphate removal (initial concentration 3 g L(-1)). Each mixture was made up of four main functional components: a mix of organic sources for bacterial growth, a neutralizing agent, a porous medium and zero-valent iron. The best mixture among the tested ones (M8: 6% leaves, 9% compost, 3% zero-valent iron, 30% silica sand, 30% perlite, 22% limestone) presented optimal conditions for SRB growth (pH 7.8 +/- 0.1; E(h)= -410 +/- 5 mV) and 83% sulphate removal in 22 days (25% due to bioreduction, 32% due to sorption onto compost and 20% onto leaves). M8 mixture allowed the complete abatement of cadmium with a significant contribution of sorption over bioprecipitation (6% Cd removal due to SRB activity). Sorption properties, characterised by potentiometric titrations and related modelling, were mainly due to carboxylic sites of organic components used in reactive mixtures. PMID:19505754

  19. Cysteine-induced modifications of zero-valent silver nanomaterials: implications for particle surface chemistry, aggregation, dissolution, and silver speciation.

    PubMed

    Gondikas, Andreas P; Morris, Amanda; Reinsch, Brian C; Marinakos, Stella M; Lowry, Gregory V; Hsu-Kim, Heileen

    2012-07-01

    The persistence of silver nanoparticles in aquatic environments and their subsequent impact on organisms depends on key transformation processes, which include aggregation, dissolution, and surface modifications by metal-complexing ligands. Here, we studied how cysteine, an amino acid representative of thiol ligands that bind monovalent silver, can alter the surface chemistry, aggregation, and dissolution of zero-valent silver nanoparticles. We compared nanoparticles synthesized with two coatings, citrate and polyvinylpirrolidone (PVP), and prepared nanoparticle suspensions (approximately 8 μM total Ag) containing an excess of cysteine (400 μM). Within 48 h, up to 47% of the silver had dissolved, as indicated by filtration of the samples with a 0.025-μm filter. Initial dissolution rates were calculated from the increase of dissolved silver concentration when particles were exposed to cysteine and normalized to the available surface area of nanoparticles in solution. In general, the rates of dissolution were almost 3 times faster for citrate-coated nanoparticles relative to PVP-coated nanoparticles. Rates tended to be slower in solutions with higher ionic strength in which the nanoparticles were aggregating. X-ray absorption spectroscopy analysis of the particles suggested that cysteine adsorbed to silver nanoparticles surfaces through the formation of Ag(+I)--sulfhydryl bonds. Overall, the results of this study highlight the importance of modifications by sulfhydryl-containing ligands that can drastically influence the long-term reactivity of silver nanoparticles in the aquatic environment and their bioavailability to exposed organisms. Our findings demonstrate the need to consider multiple interlinked transformation processes when assessing the bioavailability, environmental risks, and safety of nanoparticles, particularly in the presence of metal-binding ligands. PMID:22448900

  20. Investigating the potential for long-term permeable reactive barrier (PRB) monitoring from the electrical signatures associated with the reduction in reactive iron performance

    SciTech Connect

    Slater, Lee D.; Korte, N.; Baker, J.

    2005-12-14

    The objective of this work was to conduct laboratory and field experiments to determine the sensitivity of low frequency electrical measurements (resistivity and induced polarization) to the processes of corrosion and precipitation that are believed to limit permeable reactive barrier (PRB) performance. The research was divided into four sets of experiments that were each written up and submitted to a peer-reviewed journal: [1] A laboratory experiment to define the controls of aqueous chemistry (electrolyte activity; pH; valence) and total zero valent iron (Fe0) available surface area on the electrical properties of Fe0 columns. [2] A laboratory experiment to determine the impact of corrosion and precipitation on the electrical response of synthetic Fe0 columns as a result of geochemical reactions with NaSO4 and NaCO3 electrolytes. [3] Laboratory experiments on a sequence of cores retrieved from the Kansas City PRB to determine the magnitude of electrical and geochemical changes within a field active PRB after eight years of operation [4] Field-scale cross borehole resistivity and induced polarization monitoring of the Kansas City PRB to evaluate the potential of electrical imaging as a technology for non-invasive, long-term monitoring of indicators of reduced PRB performance This report first summarizes the findings of the four major experiments conducted under this research. The reader is referred to the four papers in Appendices 1-4 for a full description of each experiment, including motivation and significance, technical details, findings and implications. The deliverables of the project, including the publications, conference papers and new collaborative arrangements that have resulted are then described. Appendices 5-6 contain two technical reports written by co-PI Korte describing (1) supporting geochemical measurements, and (2) the coring procedure, conducted at the Kansas City PRB as part of this project.

  1. 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...

  2. Experimental design and response surface modelling for optimization of vat dye from water by nano zero valent iron (NZVI).

    PubMed

    Arabi, Simin; Sohrabi, Mahmoud Reza

    2013-01-01

    In this study, NZVI particles was prepared and studied for the removal of vat green 1 dye from aqueous solution. A four-factor central composite design (CCD) combined with response surface modeling (RSM) to evaluate the combined effects of variables as well as optimization was employed for maximizing the dye removal by prepared NZVI based on 30 different experimental data obtained in a batch study. Four independent variables, viz. NZVI dose (0.1-0.9 g/L), pH (1.5-9.5), contact time (20-100 s), and initial dye concentration (10-50 mg/L) were transform to coded values and quadratic model was built to predict the responses. The significant of independent variables and their interactions were tested by the analysis of variance (ANOVA). Adequacy of the model was tested by the correlation between experimental and predicted values of the response and enumeration of prediction errors. The ANOVA results indicated that the proposed model can be used to navigate the design space. Optimization of the variables for maximum adsorption of dye by NZVI particles was performed using quadratic model. The predicted maximum adsorption efficiency (96.97%) under the optimum conditions of the process variables (NZVI dose 0.5 g/L, pH 4, contact time 60 s, and initial dye concentration 30 mg/L) was very close to the experimental value (96.16%) determined in batch experiment. In the optimization, R2 and R2adj correlation coefficients for the model were evaluated as 0.95 and 0.90, respectively. PMID:24362989

  3. 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(23C) range (from 7 to 12) and temperature (23 to 90C) 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.

  4. Total aerobic destruction of azo contaminants with nanoscale zero-valent copper at neutral pH: promotion effect of in-situ generated carbon center radicals.

    PubMed

    Dong, Guohui; Ai, Zhihui; Zhang, Lizhi

    2014-12-01

    In this study, nanoscale zero-valent copper (nZVC) was synthesized with a facile solvothermal method and used for the aerobic removal of azo contaminants at neutral pH for the first time. We found that both Cu(I) and OH generated during the nZVC induced molecular oxygen activation process accounted for the rapid total destruction of azo contaminants in the nZVC/Air system, where nZVC could activate molecular oxygen to produce H2O2, and also release Cu(I) to break the -NN- bond of azo contaminants via the sandmeyer reaction for the generation of carbon center radicals. The in-situ generated carbon center radicals would then react with OH produced by the Cu(I) catalyzed decomposition of H2O2, resulting in the generation of low molecular weight organic acids and their subsequent mineralization. The indispensible role of Cu(I) catalyzed sandmeyer reaction and the promotion effect of in-situ generated carbon center radicals on the rapid total destruction of azo contaminants in the nZVC/Air system were confirmed by gas chromatography-mass spectrometry analysis. This study can deepen our understanding on the degradation of organic pollutant with molecular oxygen activated by zero valent metal, and also provide a new method to remove azo contaminants at neutral pH. PMID:25181614

  5. Selected hydrologic data for the field demonstration of three permeable reactive barriers near Fry Canyon, Utah, 1996-2000

    USGS Publications Warehouse

    Wilkowske, Chris D.; Rowland, Ryan C.; Naftz, David L.

    2001-01-01

    Three permeable reactive barriers (PRBs) were installed near Fry Canyon, Utah, in August 1997 to demonstrate the use of PRBs to control the migration of uranium in ground water. Reactive material included (1) bone-char phosphate, (2) zero-valent iron pellets, and (3) amorphous ferric oxyhydroxide coated gravel. An extensive monitoring network was installed in and around each PRB for collection of water samples, analysis of selected water-quality parameters, and monitoring of water levels. Water temperature, specific conductance, pH, Eh (oxidation-reduction potential), and dissolved oxygen were measured continuously within three different barrier materials, and in two monitoring wells. Water temperature and water level below land surface were electronically recorded every hour with pressure transducers. Data were collected from ground-water monitoring wells installed in and around the PRBs during 1996-98 and from surface-water sites in Fry Creek.

  6. Iron Hydroxy Carbonate Formation in Zerovalent Iron Permeable Reactive Barriers: Characterization and Evaluation of Phase Stability

    EPA Science Inventory

    Predicting the long-term potential of permeable reactive barriers for treating contaminated groundwater relies on understanding the endpoints of biogeochemical reactions between influent groundwater and the reactive medium. Iron hydroxy carbonate (chukanovite) is frequently obs...

  7. Integrated evaluation of the performance of a more than seven year old permeable reactive barrier at a site contaminated with chlorinated aliphatic hydrocarbons (CAHs).

    PubMed

    Muchitsch, Nanna; Van Nooten, Thomas; Bastiaens, Leen; Kjeldsen, Peter

    2011-11-01

    An important issue of concern for permeable reactive iron barriers is the long-term efficiency of the barriers due to the long operational periods required. Mineral precipitation resulting from the anaerobic corrosion of the iron filings and bacteria present in the barrier may play an important role in the long-term performance. An integrated study was performed on the Vapokon permeable reactive barrier (PRB) in Denmark by groundwater and iron core sample characterization. The detailed field groundwater sampling carried out from more than 75 well screens up and downstream the barrier showed a very efficient removal (>99%) for the most important CAHs (PCE, TCE and 1,1,1-TCA). However, significant formation of cis-DCE within the PRB resulted in an overall insufficient efficiency for cis-DCE removal. The detailed analysis of the upstream groundwater revealed a very heterogeneous spatial distribution of contaminant loading into the PRB, which resulted in that only about a quarter of the barrier system is treating significant loads of CAHs. Laboratory batch experiments using contaminated groundwater from the site and iron material from the core samples revealed that the aged iron material performed equally well as virgin granular iron of the same type based on determined degradation rates despite that parts of the cored iron material were covered by mineral precipitates (especially iron sulfides, carbonate green rust and aragonite). The PCR analysis performed on the iron core samples indicated the presence of a microbial consortium in the barrier. A wide range of species were identified including sulfate and iron reducing bacteria, together with Dehalococcoides and Desulfuromonas species indicating microbial reductive dehalogenation potential. The microbes had a profound effect on the performance of the barrier, as indicated by significant degradation of dichloromethane (which is typically unaffected by zero valent iron) within the barrier. PMID:22115091

  8. SURFACE-ALTERED ZEOLITES AS PERMEABLE BARRIERS FOR IN SITU TREATMENT OF CONTAMINATED GROUNDWATER

    SciTech Connect

    Robert S. Bowman; Pengfei Zhang; Xian Tao

    2002-03-01

    This report summarizes experiments to develop and test surfactant-modified zeolite/zero-valent iron (SMZ/ZVI) pellets for permeable reactive barriers to treat groundwater contamination. Coating a glass foam core with a mixture of hexadecyltrimethylammonium surfactant, zeolite, and ZVI produced a high hydraulic conductivity, mechanically stable pellet. Laboratory experiments showed that the pellets completely removed soluble chromate from aqueous solution, and reduced perchloroethylene (PCE) concentrations more than pellets that lacked surfactant. Based upon the laboratory results, they predicted a 1-m-wide SMZ/ZVI barrier that would reduce PCE concentrations by four orders of magnitude. Thirteen cubic meters (470 cubic feet) of SMZ/ZVI pellets were manufactured and emplaced in a permeable barrier test facility. A controlled plume of chromate and PCE was allowed to contact the barrier for four weeks. The entire plume was captured by the barrier. No chromate was detected downgradient of the barrier. The PCE broke through the barrier after four weeks, and downgradient concentrations ultimately exceeded 10% of the influent PCE. The less-than-expected PCE reduction was attributed to insufficient surfactant content, the large size, and pH-altering characteristics of the bulk-produced pellets. The pellets developed here can be improved to yield a performance- and cost-competitive permeable barrier material.

  9. Formation Processes and Impacts of Reactive and Nonreactive Minerals in Permeable Reactive Barriers

    EPA Science Inventory

    Mineral precipitates in zero-valent iron PRBs can be classified by formation processes into three groups: 1) those that result from changes in chemical conditions (i.e., changes in pH, e.g., calcite); 2) those that are a consequence of microbial activity (i.e., sulfate reduction,...

  10. FORMATION PROCESSES AND CONSEQUENCES OF REACTIVE AND NON-REACTIVE MINERAL PRECIPITATES IN PERMEABLE REACTIVE BARRIERS

    EPA Science Inventory

    Mineral precipitates in zero-valent iron PRBs can be classified by formation processes into three groups: 1) those that result from changes in chemical conditions (i.e., change in pH, e.g., calcite); 2) those that are a consequence of microbial activity (i.e., sulfate reduction, ...

  11. PERMEABLE REACTIVE BARRIER STRATEGIES FOR REMEDIATION OF ARSENIC-CONTAMINATED GROUNDWATER

    EPA Science Inventory

    Results are presented from laboratory batch tests using zero-valent iron to treat arsenic-contaminated groundwater. The laboratory tests were conducted using near- neutral pH groundwater from a contaminated aquifer located adjacent to a custom smelting facility. Experiments we...

  12. 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...

  13. Iron(II,III)-polyphenol complex nanoparticles derived from green tea with remarkable ecotoxicological impact

    EPA Science Inventory

    There are several greener methods exist to synthesize zerovalent iron nanoparticles (nZVI) using different bio-based reducing agents. Although their useful properties in degradation of organic dyes, chlorinated organics, or arsenic have been described earlier, their characteriza...

  14. 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...

  15. SPATIAL AND TEMPORAL TRENDS IN GROUNDWATER CHEMISTRY AND PRECIPITATE FORMATION AT THE ELIZABETH CITY PERMEABLE REACTIVE BARRIER

    EPA Science Inventory

    Accumulation of mineral precipitates and microbial biomass are key factors that impact the long-term performance of PRBs. Both processes can impact remedial performance by affecting zero-valent iron reactivity and permeability. Results will be presented from solid-phase and gro...

  16. APPLICATIONS OF SURFACE ANALYSIS IN THE ENVIRONMENTAL SCIENCES: DEHALOGENATION OF CHLOROCARBONS WITH ZERO-VALENT IRON AND IRON-CONTAINING MINERAL SURFACES. (R828164)

    EPA Science Inventory

    Halogenated organic compounds are common pollutants in groundwater. Consequently, there is widespread interest in understanding the reactions of these compounds in the environment and developing remediation strategies. One area of ongoing research involves the reductive dechlo...

  17. Monitoring the removal of phosphate from ground water discharging through a pond-bottom permeable reactive barrier

    USGS Publications Warehouse

    McCobb, T.D.; LeBlanc, D.R.; Massey, A.J.

    2009-01-01

    Installation of a permeable reactive barrier to intercept a phosphate (PO4) plume where it discharges to a pond provided an opportunity to develop and test methods for monitoring the barrier's performance in the shallow pond-bottom sediments. The barrier is composed of zero-valent-iron mixed with the native sediments to a 0.6-m depth over a 1100-m2 area. Permanent suction, diffusion, and seepage samplers were installed to monitor PO 4 and other chemical species along vertical transects through the barrier and horizontal transects below and near the top of the barrier. Analysis of pore water sampled at about 3-cm vertical intervals by using multilevel diffusion and suction samplers indicated steep decreases in PO4 concentrations in ground water flowing upward through the barrier. Samples from vertically aligned pairs of horizontal multiport suction samplers also indicated substantial decreases in PO4 concentrations and lateral shifts in the plume's discharge area as a result of varying pond stage. Measurements from Lee-style seepage meters indicated substantially decreased PO4 concentrations in discharging ground water in the treated area; temporal trends in water flux were related to pond stage. The advantages and limitations of each sampling device are described. Preliminary analysis of the first 2 years of data indicates that the barrier reduced PO4 flux by as much as 95%. ?? 2009 National Ground Water Association.

  18. Investigating dominant processes in ZVI permeable reactive barriers using reactive transport modeling.

    PubMed

    Weber, Anne; Ruhl, Aki S; Amos, Richard T

    2013-08-01

    The reactive and hydraulic efficacy of zero valent iron permeable reactive barriers (ZVI PRBs) is strongly affected by geochemical composition of the groundwater treated. An enhanced version of the geochemical simulation code MIN3P was applied to simulate dominating processes in chlorinated hydrocarbons (CHCs) treating ZVI PRBs including geochemical dependency of ZVI reactivity, gas phase formation and a basic formulation of degassing. Results of target oriented column experiments with distinct chemical conditions (carbonate, calcium, sulfate, CHCs) were simulated to parameterize the model. The simulations demonstrate the initial enhancement of anaerobic iron corrosion due to carbonate and long term inhibition by precipitates (chukanovite, siderite, iron sulfide). Calcium was shown to enhance long term corrosion due to competition for carbonate between siderite, chukanovite, and aragonite, with less inhibition of iron corrosion by the needle like aragonite crystals. Application of the parameterized model to a field site (Bernau, Germany) demonstrated that temporarily enhanced groundwater carbonate concentrations caused an increase in gas phase formation due to the acceleration of anaerobic iron corrosion. PMID:23743511

  19. Investigating dominant processes in ZVI permeable reactive barriers using reactive transport modeling

    NASA Astrophysics Data System (ADS)

    Weber, Anne; Ruhl, Aki S.; Amos, Richard T.

    2013-08-01

    The reactive and hydraulic efficacy of zero valent iron permeable reactive barriers (ZVI PRBs) is strongly affected by geochemical composition of the groundwater treated. An enhanced version of the geochemical simulation code MIN3P was applied to simulate dominating processes in chlorinated hydrocarbons (CHCs) treating ZVI PRBs including geochemical dependency of ZVI reactivity, gas phase formation and a basic formulation of degassing. Results of target oriented column experiments with distinct chemical conditions (carbonate, calcium, sulfate, CHCs) were simulated to parameterize the model. The simulations demonstrate the initial enhancement of anaerobic iron corrosion due to carbonate and long term inhibition by precipitates (chukanovite, siderite, iron sulfide). Calcium was shown to enhance long term corrosion due to competition for carbonate between siderite, chukanovite, and aragonite, with less inhibition of iron corrosion by the needle like aragonite crystals. Application of the parameterized model to a field site (Bernau, Germany) demonstrated that temporarily enhanced groundwater carbonate concentrations caused an increase in gas phase formation due to the acceleration of anaerobic iron corrosion.

  20. Phosphate Barriers for Immobilization of Uranium Plumes

    SciTech Connect

    Icenhower, Jonathan P.; Burns, Peter C.

    2005-06-01

    Uranium contamination of the subsurface remains a persistent problem plaguing remedial design at sites across the U.S. that were involved with production, handling, storage, milling, and reprocessing of uranium for both civilian and defense related purposes. Remediation efforts to date have relied upon excavation, pump-and-treat, or passive remediation barriers (PRB?s) to remove or attenuate uranium mobility. Documented cases convincingly demonstrate that excavation and pump-and-treat methods are ineffective for a number of highly contaminated sites. There is growing concern that use of conventional PRB's, such as zero-valent iron, may be a temporary solution to a problem that will persist for thousands of years. Alternatives to the standard treatment methods are therefore warranted. The core objective of our research is to demonstrate that a phosphorous amendment strategy will result in a reduction of dissolved uranium to below the proposed drinking water standard. Our hypothesis is that long-chain sodium polyphosphate compounds forestall precipitation of sparingly soluble uranyl phosphate compounds, which is paramount to preventing fouling of wells at the point of injection.

  1. Phosphate Barriers for Immobilization of Uranium Plumes

    SciTech Connect

    Burns, Peter C.

    2004-12-01

    Uranium contamination of the subsurface remains a persistent problem plaguing remedial design at sites across the U.S. that were involved with production, handling, storage, milling, and reprocessing of uranium for both civilian and defense related purposes. Remediation efforts to date have relied upon excavation, pump-and-treat, or passive remediation barriers (PRB?s) to remove or attenuate uranium mobility. Documented cases convincingly demonstrate that excavation and pump-and-treat methods are ineffective for a number of highly contaminated sites. There is growing concern that use of conventional PRB?s, such as zero-valent iron, may be a temporary solution to a problem that will persist for thousands of years. Alternatives to the standard treatment methods are therefore warranted. The core objective of our research is to demonstrate that a phosphorus amendment strategy will result in a reduction of dissolved uranium to below the proposed drinking water standard. Our hypothesis is that long-chain sodium polyphosphate compounds forestall precipitation of sparingly soluble uranyl phosphate compounds, which is paramount to preventing fouling of wells at the point of injection.

  2. 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...

  3. Treatment of inorganic contaminants using permeable reactive barriers

    NASA Astrophysics Data System (ADS)

    Blowes, David W.; Ptacek, Carol J.; Benner, Shawn G.; McRae, Che W. T.; Bennett, Timothy A.; Puls, Robert W.

    2000-09-01

    Permeable reactive barriers are an emerging alternative to traditional pump and treat systems for groundwater remediation. This technique has progressed rapidly over the past decade from laboratory bench-scale studies to full-scale implementation. Laboratory studies indicate the potential for treatment of a large number of inorganic contaminants, including As, Cd, Cr, Cu, Hg, Fe, Mn, Mo, Ni, Pb, Se, Tc, U, V, NO 3, PO 4 and SO 4. Small-scale field studies have demonstrated treatment of Cd, Cr, Cu, Fe, Ni, Pb, NO 3, PO 4 and SO 4. Permeable reactive barriers composed of zero-valent iron have been used in full-scale installations for the treatment of Cr, U, and Tc. Solid-phase organic carbon in the form of municipal compost has been used to remove dissolved constituents associated with acid-mine drainage, including SO 4, Fe, Ni, Co and Zn. Dissolved nutrients, including NO 3 and PO 4, have been removed from domestic septic-system effluent and agricultural drainage.

  4. Iron hydroxy carbonate formation in zerovalent iron permeable reactive barriers: Characterization and evaluation of phase stability

    SciTech Connect

    Wilkin, Richard T.; Lee, T.R.

    2010-10-22

    Predicting the long-term potential of permeable reactive barriers for treating contaminated groundwater relies on understanding the endpoints of biogeochemical reactions between influent groundwater and the reactive medium. Iron hydroxy carbonate (chukanovite) is frequently observed as a secondary mineral precipitate in granular iron PRBs. Mineralogical characterization was carried out using X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, and X-ray absorption spectroscopy on materials collected from three field-based PRBs in the US (East Helena, MT; Elizabeth City, NC; Denver Federal Center, CO). These PRBs were installed to treat a range of contaminants, including chlorinated organics, hexavalent chromium, and arsenic. Results obtained indicate that chukanovite is a prevalent secondary precipitate in the PRBs. Laboratory experiments on high-purity chukanovite separates were carried out to constrain the room-temperature solubility for this mineral. An estimated Gibbs energy of formation ({Delta}{sub f}G{sup o}) for chukanovite is - 1174.4 {+-} 6 kJ/mol. A mineral stability diagram is consistent with observations from the field. Water chemistry from the three reactive barriers falls inside the predicted stability field for chukanovite, at inorganic carbon concentrations intermediate to the stability fields of siderite and ferrous hydroxide. These new data will aid in developing better predictive models of mineral accumulation in zerovalent iron PRBs.

  5. Geomicrobiological Regeneration of Iron Sulfides in Engineered barrier Systems

    NASA Astrophysics Data System (ADS)

    Vannela, R.; Adriaens, P.; Hayes, K. F.

    2005-12-01

    The reactive capacity of iron sulfide-based permeable reactive barriers (PRB) to complex and co-precipitate heavy metal ions from groundwater will depend on the potential for regeneration of reactive FeS during the expected lifetime of the PRB. FeS reactivity may decrease in a PRB in time as the result of the following processes: (i) oxidation of FeS and the formation of ferric iron (Fe(III)) oxide solids in the presence of oxygenated groundwater at the entrance of the PRB, (ii) oxidation of FeS in the presence of redox active metals like As(V) with the formation of ferric solids, (iii) co-precipitation of heavy metals within the PRB with the reactive FeS leading to the formation of insoluble metal sulfides co-precipitates with the concomitant release of ferrous iron and formation of ferrous (Fe(II) oxide, hydroxide, or carbonate solids, (iv) clogging of the PRB structure due to formation of precipitate products from processes (i) - (iii).. We have demonstrated the formation of triolite in the presence of an oxidized form of hydrous ferric oxide (HFO), various sulfate concentrations, and biomass densities for the sulfate reducing bacterium (SRB) Desulfovibrio vulgaris. This result has allowed us to demonstrate the feasibility of regeneration of FeS from the ferric oxide and hydroxide solids that may be produced under scenarios (i) and (ii) above as well as to establish the electron donor and acceptor requirements for this SRB. Using Desulfobacterium autotrophicum, both HFO and soluble complexed forms of ferric iron gave rise to the formation of mackinawite. The latter have been shown to react with As (V) and Cd (II) to form ferric solids. Both organisms will be used to generate FeS solids in the presence of crystalline forms of ferric solids expected to form from scenarios (i) and (ii) (e.g., goethite and the mixed Fe(II)/(Fe(III) magnetite, and green rusts) and ferrous iron solids from scenarios (iii) and (iv) (Fe(II) oxides and siderite). Similar to the study completed on HFO and ferric citrate, the FeS solids will be characterized in terms of structure (XRD), conversion efficiency to FeS, and subsequent reactivity in batch systems to As and Cd.

  6. Field Studies of the Electrical Properties of Permeable Reactive Barriers for Monitoring Barrier Aging

    NASA Astrophysics Data System (ADS)

    Sharpe, R.; Labrecque, D. J.; Slater, L.

    2006-12-01

    Permeable reactive barriers (PRB) are a promising technology for the remediation of groundwater containing a range of organic and inorganic contaminants. Although there are number of different types of reactive barriers, some of the most important are constructed from granular zero valent iron (ZVI). One challenge in the large- scale, long-term implementation of PRBs is to monitor the change in barrier properties over time. For example, mineral precipitates can reduce the effectiveness of the barrier by either insulating the reaction surfaces of the ZVI particles and/or by filling the pore space in the barrier and thus reducing its hydraulic permeability. Previous research has shown that resistivity and induced polarization (IP) measurements are sensitive to corrosion and precipitation due to redox reactions between ions in solution and the ZVI mineral surface. New field studies, supported by additional laboratory studies appear to confirm this work. Resisitivity and IP surveys were conducted at a total of seven barriers at four different sites: the Denver Federal Center; Monticello, Utah; the Kansas City, Missouri Department of Energy site, and the Asarco Smelter Site in East Helena, Montana. These surveys used combinations of surface and borehole surveys to characterized barriers. The surveys are repeated at approximately six-month intervals to provide information on temporal changes. In addition, surveys at the Kansas City barrier followed up on earlier research by providing several years of historical data and a new barrier at East Helena Montana has been instrumented with an autonomous monitoring system allowing continuous monitoring of the barrier electrical properties. Results show an increase in both real and imaginary conductivity as barriers age. For new barriers, the conductivity of ZVI is typically a few tens of mS/m, only modestly higher than that of the background sediments surrounding the barrier. For heavily altered barriers such as the Monticello, Utah barrier, the conductivity is typically tens of S/m, a thousand times higher the unaltered barriers. Field values of chargeability (measured using a 1 Hz primary waveform and an integration window centered at 40 ms) also tend to increase from roughly a 100 mV/V at the East Helena Barrier to about 300 mV/V at Monticello. Other sites tend to be intermediate between these extremes.

  7. 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

  8. 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.

  9. 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

  10. 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) ...

  11. Predicting longevity of iron permeable reactive barriers using multiple iron deactivation models

    NASA Astrophysics Data System (ADS)

    Carniato, L.; Schoups, G.; Seuntjens, P.; Van Nooten, T.; Simons, Q.; Bastiaens, L.

    2012-11-01

    In this study we investigate the model uncertainties involved in predicting long-term permeable reactive barrier (PRB) remediation efficiency based on a lab-scale column experiment under accelerated flow conditions. A PRB consisting of 20% iron and 80% sand was simulated in a laboratory-scale column and contaminated groundwater was pumped into the column for approximately 1 year at an average groundwater velocity of 3.7E - 1 m d- 1. Dissolved contaminants (PCE, TCE, cis-DCE, trans-DCE and VC) and inorganic (Ca2 +, Fe2 +, TIC and pH) concentrations were measured in groundwater sampled at different times and at eight different distances along the column. These measurements were used to calibrate a multi-component reactive transport model, which subsequently provided predictions of long-term PRB efficiency under reduced flow conditions (i.e., groundwater velocity of 1.4E - 3 m d- 1), representative of a field site of interest in this study. Iron reactive surface reduction due to mineral precipitation and iron dissolution was simulated using four different models. All models were able to reasonably well reproduce the column experiment measurements, whereas the extrapolated long-term efficiency under different flow rates was significantly different between the different models. These results highlight significant model uncertainties associated with extrapolating long-term PRB performance based on lab-scale column experiments. These uncertainties should be accounted for at the PRB design phase, and may be reduced by independent experiments and field observations aimed at a better understanding of reactive surface deactivation mechanisms in iron PRBs.

  12. 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

  13. Remediation of arsenic-contaminated groundwater using media-injected permeable reactive barriers with a modified montmorillonite: sand tank studies.

    PubMed

    Luo, Ximing; Liu, Haifei; Huang, Guoxin; Li, Ye; Zhao, Yan; Li, Xu

    2016-01-01

    A modified montmorillonite (MMT) was prepared using an acid activation-sodium activation-iron oxide coating method to improve the adsorption capacities of natural MMTs. For MMT, its interlamellar distance increased from 12.29 to 13.36 Å, and goethite (α-FeOOH) was intercalated into its clay layers. Two novel media-injected permeable reactive barrier (MI-PRB) configurations were proposed for removing arsenic from groundwater. Sand tank experiments were conducted to investigate the performance of the two MI-PRBs: Tank A was filled with quartz sand. Tank B was packed with quartz sand and zero-valent iron (ZVI) in series, and the MMT slurry was respectively injected into them to form reactive zones. The results showed that for tank A, total arsenic (TA) removal of 98.57 % was attained within the first 60 mm and subsequently descended slowly to 88.84 % at the outlet. For tank B, a similar spatial variation trend was observed in the quartz sand layer, and subsequently, TA removal increased to ≥99.80 % in the ZVI layer. TA removal by MMT mainly depended on both surface adsorption and electrostatic adhesion. TA removal by ZVI mainly relied on coagulation/precipitation and adsorption during the iron corrosion. The two MI-PRBs are feasible alternatives for in situ remediation of groundwater with elevated As levels. PMID:26347414

  14. Iron serves as diffusion barrier in thermally regenerative galvanic cell

    NASA Technical Reports Server (NTRS)

    Crouthamel, C. E.

    1967-01-01

    Pure iron or iron-coated diaphragm provides a hydrogen diffusion electrode for a thermally regenerative galvanic cell. It allows the gas to diffuse through its interatomic spaces and resists the corrosive action of the cell environment.

  15. In-situ Pb(2+) remediation using nano iron particles.

    PubMed

    Tehrani, Mohammad Reza Fadaei; Shamsai, Abolfazl; Vossughi, Manoochehr

    2015-01-01

    Originally, application of nano zero valent iron (nZVI) particles for the removal of lead (Pb(2+)) in porous media was studied. At first, stabilized nZVI (S-nZVI) was prepared and characterized, then used in batch and continuous systems. Based on the batch experiments, corresponding reaction kinetics well fitted with the pseudo-first-order adsorption model, and reaction rate ranged from 0.01 to 0.04 g/mg/min depend on solution pH and the molar ratio between Fe and Pb. In batch tests, optimal condition with more than 90% removal efficiency at 60 min was observed at a pH range of 4 to 6 and Fe/Pb ratio more than 2.5. Continuous experiments exposed that Pb(2+) remediation was as well influenced by seepage velocity, grain size, and type of porous media. The maximum Pb(2+) removal efficiency in batch and bench-scale systems were 97% and 81%, correspondingly. The results have shown the ability of S-nZVI to use in permeable reactive barriers, as an efficient adsorbent for Pb(2+), because of its excellent stability, high reducing power, and a large surface area. PMID:25763187

  16. Tracer method to determine residence time in a permeable reactive barrier.

    PubMed

    Bartlett, T R; Morrison, S J

    2009-01-01

    A method is presented to evaluate ground water residence time in a zero-valent iron (ZVI) permeable reactive barrier (PRB) using radon-222 ((222)Rn) as a radioactive tracer. Residence time is a useful indicator of PRB hydraulic performance, with application to estimating the volumetric rate of ground water flow through a PRB, identifying flow heterogeneity, and characterizing flow conditions over time as a PRB matures. The tracer method relies on monitoring the decay of naturally occurring aqueous (222)Rn as ground water flows through a PRB. Application of the method at a PRB site near Monticello, Utah, shows that after 8 years of operation, residence times in the ZVI range from 80 to 486 h and correlate well with chemical parameters (pH, Ca, SO(4), and Fe) that indicate the relative residence time. Residence times in this case study are determined directly from the first-order decay equation because we show no significant emanation of (222)Rn within the PRB and no measurable loss of (222)Rn other than by radioactive decay. PMID:19245377

  17. Phosphate Barriers for Immobilization of Uranium Plumes

    SciTech Connect

    Burns, Peter C.

    2005-06-01

    Uranium contamination of the subsurface has remained a persistent problem plaguing remedial design at sites across the U.S. that were involved with production, handling, storage, milling, and reprocessing of fissile uranium for both civilian and defense related purposes. Remediation efforts to date have relied upon excavation, pump-and-treat, or passive remediation barriers (PRB's) to remove or attenuate uranium mobility. Documented cases convincingly demonstrate that excavation and pump-and-treat methods are ineffective for a number of highly contaminated sites. There is growing concern that use of conventional PRB?s, such as zero-valent iron, are a temporary solution to a problem that will persist for thousands of years. Alternatives to the standard treatment methods are therefore warranted. The core objective of our research is to demonstrate that a phosphorus amendment strategy will result in a reduction of dissolved uranium to below the proposed drinking water standard. Our hypothesis is that long-chain polyphosphate compounds forestall precipitation of sparingly soluble uranyl phosphate compounds, which is key to preventing fouling of wells at the point of injection. Our other fundamental objective is to synthesize and correctly characterize the uranyl phosphate phases that form in the geochemical conditions under consideration. This report summarizes work conducted at the University of Notre Dame through November of 2003 under DOE grant DE-FG07-02ER63489, which has been funded since September, 2002. The objectives at Notre Dame are development of synthesis techniques for uranyl phosphate phases, together with detailed structural and chemical characterization of the myriad of uranyl phosphate phases that may form under geochemical conditions under consideration.

  18. GEOCHEMICAL AND MICROBIAL REACTIONS AFFECTING THE LONG-TERM PERFORMANCE OF IN SITU 'IRON BARRIERS'

    EPA Science Inventory

    The in situ application of granular iron (Fe0) has become popular for the destruction of halogenated organic compounds for the immobilization of specific metals in groundwater. However, a knowledge gap exists concerning the long-term performance of the Fe0-barriers. The corrosi...

  19. CHROMIUM REMOVAL PROCESSES DURING GROUNDWATER REMEDIATION BY A ZEROVALENT IRON PERMEABLE REACTIVE BARRIER

    EPA Science Inventory

    Solid-phase associations of chromium were examined in core materials collected from a full-scale, zerovalent iron, permeable reactive barrier (PRB) at the U.S. Coast Guard Support Center located near Elizabeth City (NC). The PRB was installed in 1996 to treat groundwater contami...

  20. Transformation of Reactive Iron Minerals in a Permeable Reactive Barrier (Biowall) Used to Treat TCE in Groundwater

    EPA Science Inventory

    Abstract: Iron and sulfur reducing conditions are generally created in permeable reactive barrier (PRB) systems constructed for groundwater treatment, which usually leads to formation of iron sulfide phases. Iron sulfides have been shown to play an important role in degrading ch...

  1. Regulation of brain iron and copper homeostasis by brain barrier systems: implication in neurodegenerative diseases.

    PubMed

    Zheng, Wei; Monnot, Andrew D

    2012-02-01

    Iron (Fe) and copper (Cu) are essential to neuronal function; excess or deficiency of either is known to underlie the pathoetiology of several commonly known neurodegenerative disorders. This delicate balance of Fe and Cu in the central milieu is maintained by the brain barrier systems, i.e., the blood-brain barrier (BBB) between the blood and brain interstitial fluid and the blood-cerebrospinal fluid barrier (BCB) between the blood and cerebrospinal fluid (CSF). This review provides a concise description on the structural and functional characteristics of the brain barrier systems. Current understanding of Fe and Cu transport across the brain barriers is thoroughly examined, with major focuses on whether the BBB and BCB coordinate the direction of Fe and Cu fluxes between the blood and brain/CSF. In particular, the mechanism by which pertinent metal transporters in the barriers, such as the transferrin receptor (TfR), divalent metal transporter (DMT1), copper transporter (CTR1), ATP7A/B, and ferroportin (FPN), regulate metal movement across the barriers is explored. Finally, the detrimental consequences of dysfunctional metal transport by brain barriers, as a result of endogenous disorders or exogenous insults, are discussed. Understanding the regulation of Fe and Cu homeostasis in the central nervous system aids in the design of new drugs targeted on the regulatory proteins at the brain barriers for the treatment of metal's deficiency or overload-related neurological diseases. PMID:22115751

  2. Regulation of Brain Iron and Copper Homeostasis by Brain Barrier Systems: Implication in Neurodegenerative Diseases

    PubMed Central

    Zheng, Wei; Monnot, Andrew D.

    2011-01-01

    Iron (Fe) and copper (Cu) are essential to neuronal function; excess or deficiency of either is known to underlie the pathoetiology of several commonly known neurodegenerative disorders. This delicate balance of Fe and Cu in the central milieu is maintained by the brain barrier systems, i.e., the blood-brain barrier (BBB) between the blood and brain interstitial fluid and the blood- cerebrospinal fluid barrier (BCB) between the blood and cerebrospinal fluid (CSF). This review provides a concise description on the structural and functional characteristics of the brain barrier systems. Current understanding of Fe and Cu transport across the brain barriers is thoroughly examined, with major focuses on whether the BBB and BCB coordinate the direction of Fe and Cu fluxes between the blood and brain/CSF. In particular, the mechanism by which pertinent metal transporters in the barriers, such as the transferrin receptor (TfR), divalent metal transporter (DMT1), copper transporter (CTR1), ATP7A/B, and ferroportin (FPN), regulate metal movement across the barriers is explored. Finally, the detrimental consequences of dysfunctional metal transport by brain barriers, as a result of endogenous disorders or exogenous insults, are discussed. Understanding the regulation of Fe and Cu homeostasis in the central nervous system aids in the design of new drugs targeted on the regulatory proteins at the brain barriers for the treatment of metals deficiency or overload-related neurological diseases. PMID:22115751

  3. Effect of Geochemical and Physical Heterogeneity on the Hanford 100D Area In Situ Redox Manipulation Barrier Longevity

    SciTech Connect

    Szecsody, Jim E.; Vermeul, Vince R.; Fruchter, Jonathan S.; Williams, Mark D.; Phillips, Jerry L.; Devary, Brooks J.; Rockhold, Mark L.; Liu, Ying

    2005-11-30

    The purpose of this study was to quantify the influence of physical and/or geochemical heterogeneities in the Hanford 100D area In Situ Redox Manipulation (ISRM) barrier, which may be contributing to the discontinuous chromate breakthrough locations along the 65-well (2,300 ft long) barrier. Possible causes of chromate breakthrough that were investigated during this study include: (1) high hydraulic conductivity zones; (2) zones of low reducible iron; and (3) high hydraulic conductivity zones with low reducible iron. This laboratory-scale investigation utilized geochemical and physical characterization data collected on 0.5 to 1 foot intervals from four borehole locations. Results of this laboratory study did not provide definitive support any of the proposed hypotheses for explaining chromate breakthrough at the Hanford 100-D Area ISRM barrier. While site characterization data indicate a significant degree of vertical variability in both physical and geochemical properties in the four boreholes investigated, lateral continuity of high conductivity/low reductive capacity zones was not observed. The one exception was at the water table, where low reductive capacity and high-K zones were observed in 3 of four boreholes. Laterally continuous high permeability zones that contain oxic sediment near the water table is the most likely explanation for high concentration chromium breakthrough responses observed at various locations along the barrier. A mechanism that could explain partial chromate breakthrough in the ISRM barrier is the relationship between the field reductive capacity and the rate of chromate oxidation. Subsurface zones with low reductive capacity still have sufficient ferrous iron mass to reduce considerable chromate, but the rate of chromate reduction slows by 1 to 2 orders of magnitude relative to sediments with moderate to high reductive capacity. The original barrier longevity estimate of 160 pore volumes for homogeneous reduced sediment, or approximately 20 years, (with 5 mg/L dissolved oxygen and 2 ppm chromate) is reduced to 85 pore volumes (10 years) when the wide spread 60 ppm nitrate plume is included in the calculation. However, this reduction in barrier lifetime is not as great for high permeability channels, as there is insufficient time to reduce nitrate (and consume ferrous iron). If the cause of laterally discontinuous breakthrough of chromate along the ISRM barrier is due to oxic transport of chromate near the water table, additional dithionite treatment in these zones will not be effective. Treatment near the water table with a technology that emplaces considerable reductive capacity is needed, such as injectable zero valent iron.

  4. Effect of Geochemical and Physical Heterogeneity on the Hanford 100D Area In Situ Redox Manipulation Barrier Longevity

    SciTech Connect

    Szecsody, Jim E.; Fruchter, Jonathan S.; Phillips, Jerry L.; Rockhold, Mark L.; Vermeul, Vince R.; Williams, Mark D.; Devary, Brooks J.; Liu, Ying

    2005-12-22

    The purpose of this study was to quantify the influence of physical and/or geochemical heterogeneities in the Hanford 100D area In Situ Redox Manipulation (ISRM) barrier, which may be contributing to the discontinuous chromate breakthrough locations along the 65-well (2,300 ft long) barrier. Possible causes of chromate breakthrough that were investigated during this study include: i) high hydraulic conductivity zones; ii) zones of low reducible iron; and iii) high hydraulic conductivity zones with low reducible iron. This laboratory-scale investigation utilized geochemical and physical characterization data collected on 0.5 to 1 foot intervals from four borehole locations.Results of this laboratory study did not provide definitive support any of the proposed hypotheses for explaining chromate breakthrough at the Hanford 100-D Area ISRM barrier. While site characterization data indicate a significant degree of vertical variability in both physical and geochemical properties in the four boreholes investigated, lateral continuity of high conductivity / low reductive capacity zones was not observed. The one exception was at the water table, where low reductive capacity and high-K zones were observed in 3 of four boreholes.Laterally continuous high permeability zones that contain oxic sediment near the water table is the most likely explanation for high concentration chromium breakthrough responses observed at various locations along the barrier. A mechanism that could explain partial chromate breakthrough in the ISRM barrier is the relationship between the field reductive capacity and the rate of chromate oxidation. Subsurface zones with low reductive capacity still have sufficient ferrous iron mass to reduce considerable chromate, but the rate of chromate reduction slows by 1 to 2 orders of magnitude relative to sediments with moderate to high reductive capacity.The original barrier longevity estimate of 160 pore volumes for homogeneous reduced sediment, or approximately 20 years, (with 5 mg/L dissolved oxygen and 2 ppm chromate) is reduced to 85 pore volumes (10 years) when the wide spread 60 ppm nitrate plume is included in the calculation. However, this reduction in barrier lifetime is not as great for high permeability channels, as there is insufficient time to reduce nitrate (and consume ferrous iron). If the cause of laterally discontinuous breakthrough of chromate along the ISRM barrier is due to oxic transport of chromate near the water table, additional dithionite treatment in these zones will not be effective. Treatment near the water table with a technology that emplaces considerable reductive capacity is needed, such as injectable zero valent iron.

  5. Column test-based optimization of the permeable reactive barrier (PRB) technique for remediating groundwater contaminated by landfill leachates

    NASA Astrophysics Data System (ADS)

    Zhou, Dan; Li, Yan; Zhang, Yinbo; Zhang, Chang; Li, Xiongfei; Chen, Zhiliang; Huang, Junyi; Li, Xia; Flores, Giancarlo; Kamon, Masashi

    2014-11-01

    We investigated the optimum composition of permeable reactive barrier (PRB) materials for remediating groundwater heavily contaminated by landfill leachate, in column tests using various mixtures of zero-valent iron (ZVI), zeolite (Zeo) and activated carbon (AC) with 0.01-0.25, 3.0-5.0 and 0.7-1.0 mm grain sizes, respectively. The main contributors to the removal of organic/inorganic contaminants were ZVI and AC, and the optimum weight ratio of the three PRB materials for removing the contaminants and maintaining adequate hydraulic conductivity was found to be 5:1:4. Average reductions in chemical oxygen demand (COD) and contents of total nitrogen (TN), ammonium, Ni, Pb and 16 polycyclic aromatic hydrocarbons (PAHs) from test samples using this mixture were 55.8%, 70.8%, 89.2%, 70.7%, 92.7% and 94.2%, respectively. We also developed a systematic method for estimating the minimum required thickness and longevity of the PRB materials. A ≥ 309.6 cm layer with the optimum composition is needed for satisfactory longevity, defined here as meeting the Grade III criteria (the Chinese National Bureau of Standards: GB/T14848/93) for in situ treatment of the sampled groundwater for ≥ 10 years.

  6. Column test-based optimization of the permeable reactive barrier (PRB) technique for remediating groundwater contaminated by landfill leachates.

    PubMed

    Zhou, Dan; Li, Yan; Zhang, Yinbo; Zhang, Chang; Li, Xiongfei; Chen, Zhiliang; Huang, Junyi; Li, Xia; Flores, Giancarlo; Kamon, Masashi

    2014-11-01

    We investigated the optimum composition of permeable reactive barrier (PRB) materials for remediating groundwater heavily contaminated by landfill leachate, in column tests using various mixtures of zero-valent iron (ZVI), zeolite (Zeo) and activated carbon (AC) with 0.01-0.25, 3.0-5.0 and 0.7-1.0mm grain sizes, respectively. The main contributors to the removal of organic/inorganic contaminants were ZVI and AC, and the optimum weight ratio of the three PRB materials for removing the contaminants and maintaining adequate hydraulic conductivity was found to be 5:1:4. Average reductions in chemical oxygen demand (COD) and contents of total nitrogen (TN), ammonium, Ni, Pb and 16 polycyclic aromatic hydrocarbons (PAHs) from test samples using this mixture were 55.8%, 70.8%, 89.2%, 70.7%, 92.7% and 94.2%, respectively. We also developed a systematic method for estimating the minimum required thickness and longevity of the PRB materials. A ? 309.6 cm layer with the optimum composition is needed for satisfactory longevity, defined here as meeting the Grade III criteria (the Chinese National Bureau of Standards: GB/T14848/93) for in situ treatment of the sampled groundwater for ? 10 years. PMID:25244420

  7. Solid lipid nanoparticles loaded with iron to overcome barriers for treatment of iron deficiency anemia.

    PubMed

    Hosny, Khaled Mohamed; Banjar, Zainy Mohammed; Hariri, Amani H; Hassan, Ali Habiballah

    2015-01-01

    According to the World Health Organization, 46% of the world's children suffer from anemia, which is usually treated with iron supplements such as ferrous sulfate. The aim of this study was to prepare iron as solid lipid nanoparticles, in order to find an innovative way for alleviating the disadvantages associated with commercially available tablets. These limitations include adverse effects on the digestive system resulting in constipation and blood in the stool. The second drawback is the high variability in the absorption of iron and thus in its bioavailability. Iron solid lipid nanoparticles (Fe-SLNs) were prepared by hot homogenization/ultrasonication. Solubility of ferrous sulfate in different solid lipids was measured, and effects of process variables such as the surfactant type and concentration, homogenization and ultrasonication times, and charge-inducing agent on the particle size, zeta potential, and encapsulation efficiency were determined. Furthermore, in vitro drug release and in vivo pharmacokinetics were studied in rabbits. Results indicated that Fe-SLNs consisted of 3% Compritol 888 ATO, 1% Lecithin, 3% Poloxamer 188, and 0.2% dicetylphosphate, with an average particle size of 25 nm with 92.3% entrapment efficiency. In vivo pharmacokinetic study revealed more than fourfold enhanced bioavailability. In conclusion, Fe-SLNs could be a promising carrier for iron with enhanced oral bioavailability. PMID:25609917

  8. Solid lipid nanoparticles loaded with iron to overcome barriers for treatment of iron deficiency anemia

    PubMed Central

    Hosny, Khaled Mohamed; Banjar, Zainy Mohammed; Hariri, Amani H; Hassan, Ali Habiballah

    2015-01-01

    According to the World Health Organization, 46% of the world’s children suffer from anemia, which is usually treated with iron supplements such as ferrous sulfate. The aim of this study was to prepare iron as solid lipid nanoparticles, in order to find an innovative way for alleviating the disadvantages associated with commercially available tablets. These limitations include adverse effects on the digestive system resulting in constipation and blood in the stool. The second drawback is the high variability in the absorption of iron and thus in its bioavailability. Iron solid lipid nanoparticles (Fe-SLNs) were prepared by hot homogenization/ultrasonication. Solubility of ferrous sulfate in different solid lipids was measured, and effects of process variables such as the surfactant type and concentration, homogenization and ultrasonication times, and charge-inducing agent on the particle size, zeta potential, and encapsulation efficiency were determined. Furthermore, in vitro drug release and in vivo pharmacokinetics were studied in rabbits. Results indicated that Fe-SLNs consisted of 3% Compritol 888 ATO, 1% Lecithin, 3% Poloxamer 188, and 0.2% dicetylphosphate, with an average particle size of 25 nm with 92.3% entrapment efficiency. In vivo pharmacokinetic study revealed more than fourfold enhanced bioavailability. In conclusion, Fe-SLNs could be a promising carrier for iron with enhanced oral bioavailability. PMID:25609917

  9. Reactive Membrane Barriers for Containment of Subsurface Contamination

    SciTech Connect

    William A. Arnold; Edward L. Cussler

    2007-02-26

    The overall goal of this project was to develop reactive membrane barriers--a new and flexible technique to contain and stabilize subsurface contaminants. Polymer membranes will leak once a contaminant is able to diffuse through the membrane. By incorporating a reactive material in the polymer, however, the contaminant is degraded or immobilized within the membrane. These processes increase the time for contaminants to breakthrough the barrier (i.e. the lag time) and can dramatically extend barrier lifetimes. In this work, reactive barrier membranes containing zero-valent iron (Fe{sup 0}) or crystalline silicotitanate (CST) were developed to prevent the migration of chlorinated solvents and cesium-137, respectively. These studies were complemented by the development of models quantifying the leakage/kill time of reactive membranes and describing the behavior of products produced via the reactions within the membranes. First, poly(vinyl alcohol) (PVA) membranes containing Fe{sup 0} and CST were prepared and tested. Although PVA is not useful in practical applications, it allows experiments to be performed rapidly and the results to be compared to theory. For copper ions (Cu{sup 2+}) and carbon tetrachloride, the barrier was effective, increasing the time to breakthrough over 300 times. Even better performance was expected, and the percentage of the iron used in the reaction with the contaminants was determined. For cesium, the CST laden membranes increased lag times more than 30 times, and performed better than theoretical predictions. A modified theory was developed for ion exchangers in reactive membranes to explain this result. With the PVA membranes, the effect of a groundwater matrix on barrier performance was tested. Using Hanford groundwater, the performance of Fe{sup 0} barriers decreased compared to solutions containing a pH buffer and high levels of chloride (both of which promote iron reactivity). For the CST bearing membrane, performance improved by a factor of three when groundwater was used in place of deionized water. The performance of high density polyethylene (HDPE) membranes containing Fe{sup 0} was then evaluating using carbon tetrachloride as the target contaminant. Only with a hydrophilic additive (glycerol), was the iron able to extend lag times. Lag times were increased by a factor of 15, but only 2-3% of the iron was used, likely due to formation of oxide precipitates on the iron surface, which slowed the reaction. With thicker membranes and lower carbon tetrachloride concentrations, it is expected that performance will improve. Previous models for reactive membranes were also extended. The lag time is a measurement of when the barrier is breached, but contaminants do slowly leak through prior to the lag time. Thus, two parameters, the leakage and the kill time, were developed to determine when a certain amount of pollutant has escaped (the kill time) or when a given exposure (concentration x time) occurs (the leakage). Finally, a model was developed to explain the behavior of mobile reaction products in reactive barrier membranes. Although the goal of the technology is to avoid such products, it is important to be able to predict how these products will behave. Interestingly, calculations show that for any mobile reaction products, one half of the mass will diffuse into the containment area and one half will escape, assuming that the volumes of the containment area and the surrounding environment are much larger than the barrier membrane. These parameters/models will aid in the effective design of barrier membranes.

  10. C, Cl and H compound-specific isotope analysis to assess natural versus Fe(0) barrier-induced degradation of chlorinated ethenes at a contaminated site.

    PubMed

    Audí-Miró, Carme; Cretnik, Stefan; Torrentó, Clara; Rosell, Mònica; Shouakar-Stash, Orfan; Otero, Neus; Palau, Jordi; Elsner, Martin; Soler, Albert

    2015-12-15

    Compound-specific isotopic analysis of multiple elements (C, Cl, H) was tested to better assess the effect of a zero-valent iron-permeable reactive barrier (ZVI-PRB) installation at a site contaminated with tetrachloroethene (PCE) and trichloroethene (TCE). The focus was on (1) using (13)C to evaluate natural chlorinated ethene biodegradation and the ZVI-PRB efficiency; (2) using dual element (13)C-(37)Cl isotopic analysis to distinguish biotic from abiotic degradation of cis-dichloroethene (cis-DCE); and (3) using (13)C-(37)Cl-(2)H isotopic analysis of cis-DCE and TCE to elucidate different contaminant sources. Both biodegradation and degradation by ZVI-PRB were indicated by the metabolites that were detected and the (13)C data, with a quantitative estimate of the ZVI-PRB efficiency of less than 10% for PCE. Dual element (13)C-(37)Cl isotopic plots confirmed that biodegradation was the main process at the site including the ZVI-PRB area. Based on the carbon isotope data, approximately 45% and 71% of PCE and TCE, respectively, were estimated to be removed by biodegradation. (2)H combined with (13)C and (37)Cl seems to have identified two discrete sources contributing to the contaminant plume, indicating the potential of δ(2)H to discriminate whether a compound is of industrial origin, or whether a compound is formed as a daughter product during degradation. PMID:26248540

  11. Mechanisms and regulation of iron trafficking across the capillary endothelial cells of the blood-brain barrier

    PubMed Central

    McCarthy, Ryan C.; Kosman, Daniel J.

    2015-01-01

    The transcellular trafficking of iron from the blood into the brain interstitium depends on iron uptake proteins in the apical membrane of brain microvascular capillary endothelial cells and efflux proteins at the basolateral, abluminal membrane. In this review, we discuss the three mechanisms by which these cells take-up iron from the blood and the sole mechanism by which they efflux this iron into the abluminal space. We then focus on the regulation of this efflux pathway by exocrine factors that are released from neighboring astrocytes. Also discussed are the cytokines secreted by capillary cells that regulate the expression of these glial cell signals. Among the interstitial factors that regulate iron efflux into the brain is the Amyloid precursor protein (APP). The role of this amyliodogenic species in brain iron metabolism is discussed. Last, we speculate on the potential relationship between iron transport at the blood-brain barrier and neurological disorders associated with iron mismanagement. PMID:26236187

  12. Automated Impedance Tomography for Monitoring Permeable Reactive Barrier Health

    SciTech Connect

    LaBrecque, D J; Adkins, P L

    2009-07-02

    The objective of this research was the development of an autonomous, automated electrical geophysical monitoring system which allows for near real-time assessment of Permeable Reactive Barrier (PRB) health and aging and which provides this assessment through a web-based interface to site operators, owners and regulatory agencies. Field studies were performed at four existing PRB sites; (1) a uranium tailing site near Monticello, Utah, (2) the DOE complex at Kansas City, Missouri, (3) the Denver Federal Center in Denver, Colorado and (4) the Asarco Smelter site in East Helena, Montana. Preliminary surface data over the PRB sites were collected (in December, 2005). After the initial round of data collection, the plan was modified to include studies inside the barriers in order to better understand barrier aging processes. In September 2006 an autonomous data collection system was designed and installed at the EPA PRB and the electrode setups in the barrier were revised and three new vertical electrode arrays were placed in dedicated boreholes which were in direct contact with the PRB material. Final data were collected at the Kansas City, Denver and Monticello, Utah PRB sites in the fall of 2007. At the Asarco Smelter site in East Helena, Montana, nearly continuous data was collected by the autonomous monitoring system from June 2006 to November 2007. This data provided us with a picture of the evolution of the barrier, enabling us to examine barrier changes more precisely and determine whether these changes are due to installation issues or are normal barrier aging. Two rounds of laboratory experiments were carried out during the project. We conducted column experiments to investigate the effect of mineralogy on the electrical signatures resulting from iron corrosion and mineral precipitation in zero valent iron (ZVI) columns. In the second round of laboratory experiments we observed the electrical response from simulation of actual field PRBs at two sites: the Kansas City barrier and the East Helena barrier. As these sites are also used for our field monitoring efforts, this allowed for a comparison between field and laboratory. In column studies with high concentrations of calcium and carbonate/bicarbonate, we observed that the increase of electrical resistivity and decrease of polarization magnitude is significant and is mainly controlled by the precipitation of calcium carbonates. In general, the electrical properties of all of the barriers studied follow a pattern. New barriers are fairly resistive with in-situ conductivity only a few times background (outside the barrier) values. Older barriers get increasingly conductive, with failed barriers showing values of over 100 S/m. The induced polarization response is more complicated. Chargeability values increase over time for young barriers, are largest for healthy barriers in the middle of their lifespan, and decrease as the barrier ages These results suggest that normalized IP appears promising as a measure of barrier age.

  13. Iron oxide cluster induced barrier-free conversion of nitric oxide to ammonia.

    PubMed

    Takahashi, Keisuke

    2015-03-01

    Nitrogen oxide (NO) conversion to ammonia (NH3) over iron oxide clusters is investigated using density functional theory calculations. The introduction of NO and H2 over gas-phase Fe4O2 results in the formation of NH3 and H2O without activation barriers. The key reaction is barrier free conversion of NO to N and H2O where the physical origin rests on negative-negative repulsion of NO over iron oxide clusters. The by-product H2O can be a hydrogen source due to electrolysis or re-visiting Fe4O2 and hence, the reaction is self-sustainable. Furthermore, the above reactions are performed by depositing Fe4O2 clusters on graphene/Cu(111) where the barrier free conversion of NO to NH3 is also observed, predicting that such reaction can be applicable. Thus, low temperature conversion of NO to NH3 over Fe4O2 can be predicted. The detailed reaction pathway and mechanism are presented. PMID:25664360

  14. Modeling porosity reductions caused by mineral fouling in continuous-wall permeable reactive barriers.

    PubMed

    Li, Lin; Benson, Craig H; Lawson, Elizabeth M

    2006-02-01

    A study was conducted to assess key factors to include when modeling porosity reductions caused by mineral fouling in permeable reactive barriers (PRBs) containing granular zero valent iron. The public domain codes MODFLOW and RT3D were used and a geochemical algorithm was developed for RT3D to simulate geochemical reactions occurring in PRBs. Results of simulations conducted with the model show that the largest porosity reductions occur between the entrance and mid-plane of the PRB as a result of precipitation of carbonate minerals and that smaller porosity reductions occur between the mid-plane and exit face due to precipitation of ferrous hydroxide. These findings are consistent with field and laboratory observations, as well as modeling predictions made by others. Parametric studies were conducted to identify the most important variables to include in a model evaluating porosity reduction. These studies showed that three minerals (CaCO3, FeCO3, and Fe(OH)2 (am)) account for more than 99% of the porosity reductions that were predicted. The porosity reduction is sensitive to influent concentrations of HCO3-, Ca2+, CO3(2-), and dissolved oxygen, the anaerobic iron corrosion rate, and the rates of CaCO3 and FeCO3 formation. The predictions also show that porosity reductions in PRBs can be spatially variable and mineral forming ions penetrate deeper into the PRB as a result of flow heterogeneities, which reflects the balance between the rate of mass transport and geochemical reaction rates. Level of aquifer heterogeneity and the contrast in hydraulic conductivity between the aquifer and PRB are the most important hydraulic variables affecting porosity reduction. Spatial continuity of aquifer hydraulic conductivity is less significant. PMID:16386821

  15. Modeling porosity reductions caused by mineral fouling in continuous-wall permeable reactive barriers

    NASA Astrophysics Data System (ADS)

    Li, Lin; Benson, Craig H.; Lawson, Elizabeth M.

    2006-02-01

    A study was conducted to assess key factors to include when modeling porosity reductions caused by mineral fouling in permeable reactive barriers (PRBs) containing granular zero valent iron. The public domain codes MODFLOW and RT3D were used and a geochemical algorithm was developed for RT3D to simulate geochemical reactions occurring in PRBs. Results of simulations conducted with the model show that the largest porosity reductions occur between the entrance and mid-plane of the PRB as a result of precipitation of carbonate minerals and that smaller porosity reductions occur between the mid-plane and exit face due to precipitation of ferrous hydroxide. These findings are consistent with field and laboratory observations, as well as modeling predictions made by others. Parametric studies were conducted to identify the most important variables to include in a model evaluating porosity reduction. These studies showed that three minerals (CaCO 3, FeCO 3, and Fe(OH) 2 (am)) account for more than 99% of the porosity reductions that were predicted. The porosity reduction is sensitive to influent concentrations of HCO 3-, Ca 2+, CO 32-, and dissolved oxygen, the anaerobic iron corrosion rate, and the rates of CaCO 3 and FeCO 3 formation. The predictions also show that porosity reductions in PRBs can be spatially variable and mineral forming ions penetrate deeper into the PRB as a result of flow heterogeneities, which reflects the balance between the rate of mass transport and geochemical reaction rates. Level of aquifer heterogeneity and the contrast in hydraulic conductivity between the aquifer and PRB are the most important hydraulic variables affecting porosity reduction. Spatial continuity of aquifer hydraulic conductivity is less significant.

  16. Backfill barriers: the use of engineered barriers based on geologic materials to assure isolation of radioactive wastes in a repository. [Nickel-iron alloys

    SciTech Connect

    Apps, J.A.; Cook, N.G.W.

    1981-06-01

    A preliminary assessment is made to show that canisters fabricated of nickel-iron alloys, and surrounded by a suitable backfill, may produce an engineered barrier where the canister material is thermodynamically stable with respect to its environment. As similar conditions exist in nature, the performance of such systems as barriers to isolate radionuclides can be predicted over very long periods, of the order of 10/sup 6/ years.

  17. Chromium-Removal Processes during Groundwater Remediation by a Zerovalent Iron Permeable Reactive Barrier

    SciTech Connect

    Wilkin, Richard T.; Su, Chunming; Ford, Robert G.; Paul, Cynthia J.

    2008-06-09

    Solid-phase associations of chromium were examined in core materials collected from a full-scale, zerovalent iron permeable reactive barrier (PRB) at the U.S. Coast Guard Support Center located near Elizabeth City, NC. The PRB was installed in 1996 to treat groundwater contaminated with hexavalent chromium. After eight years of operation, the PRB remains effective at reducing concentrations of Cr from average values >1500 {micro}g L{sup -1} in groundwater hydraulically upgradient of the PRB to values <1 {micro}g L{sup -1} in groundwater within and hydraulically downgradient of the PRB. Chromium removal from groundwater occurs at the leading edge of the PRB and also within the aquifer immediately upgradient of the PRB. These regions also witness the greatest amount of secondary mineral formation due to steep geochemical gradients that result from the corrosion of zerovalent iron. X-ray absorption near-edge structure (XANES) spectroscopy indicated that chromium is predominantly in the trivalent oxidation state, confirming that reductive processes are responsible for Cr sequestration. XANES spectra and microscopy results suggest that Cr is, in part, associated with iron sulfide grains formed as a consequence of microbially mediated sulfate reduction in and around the PRB. Results of this study provide evidence that secondary iron-bearing mineral products may enhance the capacity of zerovalent iron systems to remediate Cr in groundwater, either through redox reactions at the mineral-water interface or by the release of Fe(II) to solution via mineral dissolution and/or metal corrosion.

  18. Iron Nanoparticles for Environmental Applications Studied by Magnetic Force Microscopy

    NASA Astrophysics Data System (ADS)

    Bowman, Trevor; Inglefield, Colin; Matyjasik, Marek

    2010-10-01

    Iron nanoparticles have been widely used in environmental applications due to the ability of the iron to extract harmful chemicals from solution. Because of this trait, zero-valent, iron nanoparticles are currently being used in many water reclamation processes. Using Atomic Force Microscopy (AFM), and Magnetic Force Microscopy (MFM) with CrCo magnetic tips, we were able to obtain images of various materials with the hope to track nanoparticulate iron through different chemical reactions commonly used in water reclamation. We used standard MFM techniques in our investigation, with the magnetic information coming from a measure of the change of phase of the tip's resonant oscillation. Preliminary results of the study using commercial grade nanoparticle solutions evaporated on flat glass surfaces and plans for future experiments will be presented.

  19. Simulation of Two Strategies to Enhance Permeable Reactive Barriers in Heterogeneous Aquifer

    NASA Astrophysics Data System (ADS)

    Li, L.; Benson, C.

    2007-12-01

    Ground water flow (MODFLOW) and geochemical reactive transport models (RT3D) were used to assess the effectiveness of two strategies in limiting mineral fouling and its impact on hydraulic behavior of continuous-wall permeable reactive barriers (PRBs) employing granular zero valent iron (ZVI). A geochemical algorithm including kinetic expressions of oxidation-reduction and mineral precipitation-dissolution was developed for RT3D. The two strategies that were evaluated are (i) adding pea gravel equalization zones upgradient and down gradient of the reactive zone and (ii) placement of sacrificial pretreatment zones upgradient of the reactive zone. The PRB locates at a three-dimensional heterogeneous sandy aquifer. The sacrificial pretreatment zone contains mixtures of pea gravel and ZVI. Results of simulations show that installation of pea gravel zones provides a more conductive path for ground water flow through the ZVI, which enhances preferential flow and causes greater porosity reductions and shorter residence time in the PRB. After installation of pea gravel zones, the esidence time decreases which is caused by short travel distances in the ZVI due to short circuit of preferential flow. Sacrificial pretreatment zones can be used to elevate the ground water pH and consume many of the mineral forming ions to form secondary minerals in before the reactive zone is reached. The remaining mineral forming ions that pass into the reactive zone cause less mineral fouling. However, mineral fouling by Fe(OH)2 still occurs, and this mineral is formed regardless of the influent mineral forming ions. Addition of the sacrificial pretreatment zone slightly decreases the initial median residence time. However, the pretreatment zone retains higher residence time after 30 yrs due to less mineral fouling in the pure ZVI zone.

  20. Simulation of Two Strategies to Limit the Impact of Fouling in Permeable Reactive Barriers

    NASA Astrophysics Data System (ADS)

    Li, L.; Benson, C.

    2008-12-01

    Ground water flow (MODFLOW) and geochemical reactive transport models (RT3D) were used to assess the effectiveness of two strategies in limiting mineral fouling and its impact on hydraulic behavior of continuous- wall permeable reactive barriers (PRBs) employing granular zero valent iron (ZVI). A geochemical algorithm including kinetic expressions of oxidation-reduction and mineral precipitation-dissolution was developed for RT3D. The two strategies that were evaluated are (i) adding pea gravel equalization zones upgradient and down gradient of the reactive zone and (ii) placement of sacrificial pretreatment zones upgradient of the reactive zone. The PRB locates at a three-dimensional heterogeneous sandy aquifer. The sacrificial pretreatment zone contains mixtures of pea gravel and ZVI. Results of simulations show that installation of pea gravel zones provides a more conductive path for ground water flow through the ZVI, which enhances preferential flow and causes greater porosity reductions and shorter residence time in the PRB. After installation of pea gravel zones, the residence time decreases which is caused by short travel distances in the ZVI due to short circuit of preferential flow. Sacrificial pretreatment zones can be used to elevate the ground water pH and consume many of the mineral forming ions to form secondary minerals in before the reactive zone is reached. The remaining mineral forming ions that pass into the reactive zone cause less mineral fouling. However, mineral fouling by Fe(OH)2 still occurs, and this mineral is formed regardless of the influent mineral forming ions. Addition of the sacrificial pretreatment zone slightly decreases the initial median residence time. However, the pretreatment zone retains higher residence time after 30 yrs due to less mineral fouling in the pure ZVI zone.

  1. Ab initio study of boron in α-iron: Migration barriers and interaction with point defects

    NASA Astrophysics Data System (ADS)

    Bialon, A. F.; Hammerschmidt, T.; Drautz, R.

    2013-03-01

    Boron is a common alloying element in modern steels with a significant influence on the mechanical properties already at concentrations of only a few parts per million. The effect of boron depends on its distribution in the microstructure. Here, we characterize the elemental factors that determine the boron distribution in α-iron by density functional theory calculations. Boron as point defect has been considered in substitutional and interstitial sites. The calculated migration barriers for the substitutional and interstitial mechanisms show the first nearest-neighbor hops being preferred over second nearest-neighbor hops. A dissociative mechanism shows boron migrating via an interstitial mechanism to be likely trapped by vacancies. In order to characterize the interaction with other point defects, we determined the distance-dependent interaction energy of a boron defect with a vacancy, a second boron, and with hydrogen, carbon, nitrogen, oxygen, aluminum, silicon, phosphorus, and sulfur atoms. We find that substitutional boron binds strongly to interstitial point defects with dumbbell formation and weaker to substitutional point defects. Interstitial boron tends to repel substitutional and interstitial point defects. We find a similarity of substitutional boron and vacancies regarding their influence on elastic properties and their interaction with point defects in α-iron.

  2. Mineralogical characteristics and transformations during long-term operation of a zerovalent iron reactive barrier

    SciTech Connect

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

    2003-04-01

    Design and operation of Fe{sup 0} permeable reactive barriers (PRBs) can be improved by understanding the long-term mineralogical transformations that occur within PRBs. Changes in mineral precipitates, cementation, and corrosion of Fe{sup 0} filings within an in situ pilot-scale PRB were examined after the first 30 months of operation and compared with results of a previous study of the PRB conducted 15 months earlier using X-ray diffraction and scanning electron microscopy employing energy dispersive X-ray and backscatter electron analyses. Iron (oxy)hydroxides, aragonite, and maghemite and/or magnetite occurred throughout the cores collected 30 mo after installation. Goethite, lepidocrocite, mackinawite, aragonite, calcite, and siderite were associated with oxidized and cemented areas, while green rusts were detected in more reduced zones. Basic differences from our last detailed investigation include (i) mackinawite crystallized from amorphous FeS, (ii) aragonite transformed into calcite, (iii) akaganeite transformed to goethite and lepidocrocite, (iv) iron (oxy)hydroxides and calcium and iron carbonate minerals increased, (v) cementation was greater in the more recent study, and (vi) oxidation, corrosion, and disintegration of Fe{sup 0} filings were greater, especially in cemented areas, in the more recent study. If the degree of corrosion and cementation that was observed from 15 to 30 mo after installation continues, certain portions of the PRB (i.e., up-gradient entrance of the ground water to the Fe{sup 0} section of the PRB) may last less than five more years, thus reducing the effectiveness of the PRB to mitigate contaminants.

  3. Understanding pH Effects on Trichloroethylene and Perchloroethylene Adsorption to Iron in Permeable Reactive Barriers for Groundwater Remediation.

    PubMed

    Luo, Jing; Farrell, James

    2013-01-01

    Metallic iron filings are becoming increasing used in permeable reactive barriers for remediating groundwater contaminated by chlorinated solvents. Understanding solution pH effects on rates of reductive dechlorination in permeable reactive barriers is essential for designing remediation systems that can meet treatment objectives under conditions of varying groundwater properties. The objective of this research was to investigate how the solution pH value affects adsorption of trichloroethylene (TCE) and perchloroethylene (PCE) on metallic iron surfaces. Because adsorption is first required before reductive dechlorination can occur, pH effects on halocarbon adsorption energies may explain pH effects on dechlorination rates. Adsorption energies for TCE and PCE were calculated via molecular mechanics simulations using the Universal force field and a self-consistent reaction field charge equilibration scheme. A range in solution pH values was simulated by varying the amount of atomic hydrogen adsorbed on the iron. The potential energies associated TCE and PCE complexes were dominated by electrostatic interactions, and complex formation with the surface was found to result in significant electron transfer from the iron to the adsorbed halocarbons. Adsorbed atomic hydrogen was found to lower the energies of TCE complexes more than those for PCE. Attractions between atomic hydrogen and iron atoms were more favorable when TCE versus PCE was adsorbed to the iron surface. These two findings are consistent with the experimental observation that changes in solution pH affect TCE reaction rates more than those for PCE. PMID:23626602

  4. Understanding pH Effects on Trichloroethylene and Perchloroethylene Adsorption to Iron in Permeable Reactive Barriers for Groundwater Remediation

    PubMed Central

    Luo, Jing; Farrell, James

    2013-01-01

    Metallic iron filings are becoming increasing used in permeable reactive barriers for remediating groundwater contaminated by chlorinated solvents. Understanding solution pH effects on rates of reductive dechlorination in permeable reactive barriers is essential for designing remediation systems that can meet treatment objectives under conditions of varying groundwater properties. The objective of this research was to investigate how the solution pH value affects adsorption of trichloroethylene (TCE) and perchloroethylene (PCE) on metallic iron surfaces. Because adsorption is first required before reductive dechlorination can occur, pH effects on halocarbon adsorption energies may explain pH effects on dechlorination rates. Adsorption energies for TCE and PCE were calculated via molecular mechanics simulations using the Universal force field and a self-consistent reaction field charge equilibration scheme. A range in solution pH values was simulated by varying the amount of atomic hydrogen adsorbed on the iron. The potential energies associated TCE and PCE complexes were dominated by electrostatic interactions, and complex formation with the surface was found to result in significant electron transfer from the iron to the adsorbed halocarbons. Adsorbed atomic hydrogen was found to lower the energies of TCE complexes more than those for PCE. Attractions between atomic hydrogen and iron atoms were more favorable when TCE versus PCE was adsorbed to the iron surface. These two findings are consistent with the experimental observation that changes in solution pH affect TCE reaction rates more than those for PCE. PMID:23626602

  5. Changing the Action of Iron from Stoichiometric to Electrocatalytic in the Hydrogenation of Ketones in Aqueous Acidic Media.

    PubMed

    Gottardo, Marina; Easton, Max; Fabos, Viktoria; Guo, Si-Xuan; Zhang, Jie; Perosa, Alvise; Selva, Maurizio; Bond, Alan M; Masters, Anthony F; Maschmeyer, Thomas

    2015-11-01

    Cyclohexanone, a model compound chosen to conveniently represent small oxygenates present in the aqueous phase of biomass hydrothermal upgrading streams, was hydrogenated in the presence of electrodeposited iron(0) using aqueous formic or sulfuric acid as a hydrogen donor. Under these conditions, zero-valent iron is consumed stoichiometrically and serves as both a formic acid decomposition site and a hydrogen transfer agent. However, the resulting iron(II) can be used to continuously regenerate iron(0) when a potential is applied to the glassy carbon working electrode. Controlled potential electrolysis experiments show a 17% conversion of cyclohexanone (over 1000?seconds) to cyclohexanol with >80% efficiency of iron deposition from an iron(II) sulfate solution containing formic or sulfuric acid. In the absence of electrodeposited iron, formation of cyclohexanol could not be detected. PMID:26382111

  6. Molecular mechanism of distorted iron regulation in the blood–CSF barrier and regional blood–brain barrier following in vivo subchronic manganese exposure

    PubMed Central

    Li, G. Jane; Choi, Byung-Sun; Wang, Xueqian; Liu, Jie; Waalkes, Michael P.; Zheng, Wei

    2014-01-01

    Previous studies in this laboratory indicated that manganese (Mn) exposure in vitro increases the expression of transferrin receptor (TfR) by enhancing the binding of iron regulatory proteins (IRPs) to iron responsive element-containing RNA. The current study further tested the hypothesis that in vivo exposure to Mn increased TfR expression at both blood–brain barrier (BBB) and blood–cerebrospinal fluid (CSF) barrier (BCB), which contributes to altered iron (Fe) homeostasis in the CSF. Groups of rats (10–11 each) received oral gavages at doses of 5 mg Mn/kg or 15 mg Mn/kg as MnCl2 once daily for 30 days. Blood, CSF, and choroid plexus were collected and brain capillary fractions were separated from the regional parenchyma. Metal analyses showed that oral Mn exposure decreased concentrations of Fe in serum (−66%) but increased Fe in the CSF (+167%). Gel shift assay showed that Mn caused a dose-dependent increase of binding of IRP1 to iron responsive element-containing RNA in BCB in the choroid plexus (+70%), in regional BBB of capillaries of striatum (+39%), hippocampus (+56%), frontal cortex (+49%), and in brain parenchyma of striatum (+67%), hippocampus (+39%) and cerebellum (+28%). Real-time RT-PCR demonstrated that Mn exposure significantly increased the expression of TfR mRNA in choroid plexus and striatum with concomitant reduction in the expression of ferritin (Ft) mRNA. Collectively, these data indicate that in vivo Mn exposure results in Fe redistribution in body fluids through regulating the expression of TfR and ferritin at BCB and selected regional BBB. The disrupted Fe transport by brain barriers may underlie the distorted Fe homeostasis in the CSF. PMID:16545456

  7. Enhanced chitosan beads-supported Fe(0)-nanoparticles for removal of heavy metals from electroplating wastewater in permeable reactive barriers.

    PubMed

    Liu, Tingyi; Yang, Xi; Wang, Zhong-Liang; Yan, Xiaoxing

    2013-11-01

    The removal of heavy metals from electroplating wastewater is a matter of paramount importance due to their high toxicity causing major environmental pollution problems. Nanoscale zero-valent iron (NZVI) became more effective to remove heavy metals from electroplating wastewater when enhanced chitosan (CS) beads were introduced as a support material in permeable reactive barriers (PRBs). The removal rate of Cr (VI) decreased with an increase of pH and initial Cr (VI) concentration. However, the removal rates of Cu (II), Cd (II) and Pb (II) increased with an increase of pH while decreased with an increase of their initial concentrations. The initial concentrations of heavy metals showed an effect on their removal sequence. Scanning electron microscope images showed that CS-NZVI beads enhanced by ethylene glycol diglycidyl ether (EGDE) had a loose and porous surface with a nucleus-shell structure. The pore size of the nucleus ranged from 19.2 to 138.6 ?m with an average aperture size of around 58.6 ?m. The shell showed a tube structure and electroplating wastewaters may reach NZVI through these tubes. X-ray photoelectron spectroscope (XPS) demonstrated that the reduction of Cr (VI) to Cr (III) was complete in less than 2 h. Cu (II) and Pb (II) were removed via predominant reduction and auxiliary adsorption. However, main adsorption and auxiliary reduction worked for the removal of Cd (II). The removal rate of total Cr, Cu (II), Cd (II) and Pb (II) from actual electroplating wastewater was 89.4%, 98.9%, 94.9% and 99.4%, respectively. The findings revealed that EGDE-CS-NZVI-beads PRBs had the capacity to remediate actual electroplating wastewater and may become an effective and promising technology for in situ remediation of heavy metals. PMID:24075723

  8. Strong Pinning and Nonlinear Creep Barriers in Iron-Pnictide Superconductors

    NASA Astrophysics Data System (ADS)

    Demirdis, S.; Konczykowski, M.; van der Beek, C. J.; Prozorov, R.; Kasahara, S.; Shibauchi, T.; Matsuda, Yuji

    2011-03-01

    The irreversible magnetization of Iron-Based Superconductors is characterized by the presence of an ubiquitous peak of the critical current density jc , centered around zero field. Closer examination shows that the field-dependence of jc corresponds, in all cases, to a low-field plateau, followed by a power-law decrease, jc ~B-α (with α ~5/8 ) above a cross-over field B* . This strongly suggests that vortex pinning at low magnetic field is due to strong pinning by nanometer-scale defects. In isovalently doped materials such as BaFe 2 (As 1-x Px)2 , strong pinning is the only contribution to the critical current. The analysis of jc allows one to extract, without a priori assumptions, the elementary pinning force and the defect density. In BaFe 2 (As 1-x Px)2 , the latter quantity is in qualitative agreement with that obtained by H. Shishido et al. [Phys. Rev. Lett. 104, 057008 (2010)]. The temperature dependence of the screening current above B* is strongly affected by flux creep. The current decays as j ~ [ (kB T / U) ln (t +t0 / τ) ]- 1 / μ , with μ ~ 1.6 , showing that nonlinear creep barriers are not an exclusive feature of weak collective pinning.

  9. Assessing degradation rates of chlorinated ethylenes in column experiments with commercial iron materials used in permeable reactive barriers.

    PubMed

    Ebert, Markus; Kber, Ralf; Parbs, Anika; Plagentz, Volkmar; Schfer, Dirk; Dahmke, Andreas

    2006-03-15

    Multiple column experiments were performed using two commercial iron materials to evaluate the necessity and usefulness of preliminary investigations in permeable reactive barrier (PRB) design for chlorinated organics. Experiments were performed with contaminated groundwater and involved fresh iron granules or altered iron material excavated from PRBs. The determination of first-order rate coefficients by global nonlinear least-squares fittings indicated a variability in rate coefficients on 1 or 2 orders of magnitude. Geometric mean values of surface area normalized rate coefficients (in 10(-5) L m(-2) h(-1)) for fresh gray cast iron and iron sponge, respectively, are: tetrachloroethene (4.5, 2.6), trichloroethene (8.1, 3.3), cis-1,2-dichloroethene (3.1, 2.9), trans-1,2-dichloroethene (9.5, 5.3), 1,1-dichloroethene (4.0, 4.4), and vinyl chloride (1.6, 6.1). The increasing rate coefficients with decreasing grade of chlorination, which characterize degradation at iron sponge are linearly related to diffusion coefficients in water, suggesting diffusion limitation in the degradation process for this particular material, possibly due to a high inner surface. The variability in rate coefficients seems to be too high to use mean rate coefficients from published studies in the design procedure of PRBs, and variabilities cannot be related to groundwater characteristics, waterflow through the reactive cells, or secondary corrosion reactions. PMID:16570628

  10. Iron supplement prevents lead-induced disruption of the blood-brain barrier during rat development

    SciTech Connect

    Wang Qiang; Luo Wenjing; Zheng Wei; Liu Yiping; Xu Hui; Zheng Gang; Dai Zhongming; Zhang Wenbin; Chen Yaoming; Chen Jingyuan . E-mail: jy_chen@fmmu.edu.cn

    2007-02-15

    Children are known to be venerable to lead (Pb) toxicity. The blood-brain barrier (BBB) in immature brain is particularly vulnerable to Pb insults. This study was designed to test the hypothesis that Pb exposure damaged the integrity of the BBB in young animals and iron (Fe) supplement may prevent against Pb-induced BBB disruption. Male weanling Sprague-Dawley rats were divided into four groups. Three groups of rats were exposed to Pb in drinking water containing 342 {mu}g Pb/mL as Pb acetate, among which two groups were concurrently administered by oral gavage once every other day with 7 mg Fe/kg and 14 mg Fe/kg as FeSO{sub 4} solution as the low and high Fe treatment group, respectively, for 6 weeks. The control group received sodium acetate in drinking water. Pb exposure significantly increased Pb concentrations in blood by 6.6-folds (p < 0.05) and brain tissues by 1.5-2.0-folds (p < 0.05) as compared to controls. Under the electron microscope, Pb exposure in young animals caused an extensive extravascular staining of lanthanum nitrate in brain parenchyma, suggesting a leakage of cerebral vasculature. Western blot showed that Pb treatment led to 29-68% reduction (p < 0.05) in the expression of occludin as compared to the controls. Fe supplement among Pb-exposed rats maintained the normal ultra-structure of the BBB and restored the expression of occludin to normal levels. Moreover, the low dose Fe supplement significantly reduced Pb levels in blood and brain tissues. These data suggest that Pb exposure disrupts the structure of the BBB in young animals. The increased BBB permeability may facilitate the accumulation of Pb. Fe supplement appears to protect the integrity of the BBB against Pb insults, a beneficial effect that may have significant clinical implications.

  11. X-231A demonstration of in-situ remediation of DNAPL compounds in low permeability media by soil fracturing with thermally enhanced mass recovery or reactive barrier destruction

    SciTech Connect

    Siegrist, R.L.; Lowe, K.S.; Murdoch, L.D.; Slack, W.W.; Houk, T.C.

    1998-03-01

    The overall goal of the program of activities is to demonstrate robust and cost-effective technologies for in situ remediation of DNAPL compounds in low permeability media (LPM), including adaptations and enhancements of conventional technologies to achieve improved performance for DNAPLs in LPM. The technologies sought should be potential for application at simple, small sites (e.g., gasoline underground storage tanks) as well as at complex, larger sites (e.g., DOE land treatment units). The technologies involved in the X-231A demonstration at Portsmouth Gaseous Diffusion Plant (PORTS) utilized subsurface manipulation of the LPM through soil fracturing with thermally enhanced mass recovery or horizontal barrier in place destruction. To enable field evaluation of these approaches, a set of four test cells was established at the X-231A land treatment unit at the DOE PORTS plant in August 1996 and a series of demonstration field activities occurred through December 1997. The principal objectives of the PORTS X-231A demonstration were to: determine and compare the operational features of hydraulic fractures as an enabling technology for steam and hot air enhanced soil vapor extraction and mass recovery, in situ interception and reductive destruction by zero valent iron, and in situ interception and oxidative destruction by potassium permanganate; determine the interaction of the delivered agents with the LPM matrix adjacent to the fracture and within the fractured zone and assess the beneficial modifications to the transport and/or reaction properties of the LPM deposit; and determine the remediation efficiency achieved by each of the technology strategies.

  12. Pyrite formation by reactions of iron monosulfides with dissolved inorganic and organic sulfur species

    NASA Astrophysics Data System (ADS)

    Wilkin, R. T.; Barnes, H. L.

    1996-11-01

    Pyrite formation has been investigated at 70C and pH 6-8 by aging precipitated, disordered mackinawite, Fe 9S 8, and greigite, Fe 3S 4, in solutions containing aqueous H 2S, HS -, S x2-, S 2O 32-, SO 32-, colloidal elemental sulfur, and the organic sulfur species thiol, disulfide, and sulfonate. Pyrite formed in all experiments where unoxidized iron monosulfides were aged with species containing zero-valent sulfur, i.e., polysulfides and colloidal elemental sulfur, but not with hydrogen sulfide (or bisulfide), the sulfoxy anions, or the organic sulfur species. Pyrite formation also occurred in experiments where the starting monosulfides were air-exposed prior to aging in sulfide solutions, or when air was bubbled through a reaction vessel containing iron monosulfides suspended in a sulfid sulfide solution. The experiments indicate the rate of conversion from iron monosulfides to pyrite is not only a function of solution chemistry (i.e., pH and aqueous speciation), but also depends on the surface oxidation state of the precursor iron monosulfides. Measurements of ?34S of reactants and products from pyrite-forming experiments suggest that the conversion from iron monosulfides to pyrite may proceed via loss of ferrous iron from, rather than via addition of zero-valent sulfur to, the precursor monosulfides. The sulfur isotopic composition of pyrite in sedimentary environments should reflect the sulfur isotopic composition of the precursor iron monosulfide plus sulfur sources incorporated during surface-controlled growth processes. Pyrite forms produced in this study ranged from poorly developed octahedral grains, in experiments where initial pyritization rates were the slowest, to framboidal aggregates in experiments where initial pyritization rates were the fastest. Although greigite formation occurred in experiments that produced framboids, not all experiments that produced greigite led to framboid formation. The formation of pyrite with framboidal texture is apparently favored when iron monosulfides rapidly convert to pyrite.

  13. Degradation of trichloroethylene using iron, bimetals and trimetals.

    PubMed

    Chao, Keh-Ping; Ong, Say Kee; Fryzek, Todd; Yuan, Wanchun; Braida, Washington

    2012-01-01

    A cold, electrodeless method was used to prepare bimetals (Fe/Cu, Fe/Ni) and trimetals (Fe/Cu/Ni) for the treatment of trichloroethylene (TCE). With Fe/Cu, the degradation of TCE was observed to increase with increasing copper content up to 9.26 % (w/w) with a first-order degradation rate constant approximately 10 times faster than that of zero-valent iron (ZVI) alone. For copper content greater than 9.26 %, the TCE degradation rate decreased. Dechlorinated compounds were initially observed but they were transitory and accounted for no more than 9 % of initial TCE mass on a carbon molar basis. Ethylene was the primary end product of TCE reduction. Similarly for Fe/Ni, increasing rates of degradation were observed with increasing amounts of nickel with a maximum degradation rate constant of about 30 times higher than that of ZVI alone. However, the amount of nickel needed to reach the maximum rate was only 0.25 %. When copper and nickel were plated onto iron, the maximum reaction rate constant was approximately 50 times higher than that of ZVI. The maximum degradation of TCE was observed for a copper and nickel content of 4.17 % and 0.40 %, respectively. The experimental results indicated that TCE degradation was enhanced by more than one order of magnitude when copper and/or nickel was plated onto the zero-valent iron. However, copper or nickel plated onto iron by the elctrodeless process was found to leach out during the reaction which may, in turn, impact the contaminated water. PMID:22702813

  14. Verification and monitoring of deep granular iron permeable reactive barriers emplaced by vertical hydraulic fracturing and injection for groundwater remediation

    NASA Astrophysics Data System (ADS)

    Hubble, David Wallace

    This study evaluated the use of vertical hydraulic fracturing and injection (VHFI) to emplace granular iron as a deep passive treatment system to remove organic contaminants from groundwater at the Massachusetts Military Reservation on Cape Cod, Massachusetts. It was the first permeable reactive barrier (PRB) constructed at a depth greater than 15 m below the ground surface. VHFI propagates a vertical fracture from a slot cut through the injection-well casing at a selected depth and orientation. Granular iron is suspended in a viscous fluid using a biodegradable guar polymer and pumped through the slot to form a thin vertical sheet. Two PRBs were emplaced 6 m apart and perpendicular to the groundwater flow direction with mid-depths of about 30 m below the ground surface. Due to the depth, all of the emplacement and verification methods used down-hole tools. Resistivity imaging used salt added to the guar as an electrical tracer to map the spread of the VHFI fluid for propagation control and to estimate the extent of the completed PRB. Radar tomography before and after emplacement also provided images of the PRBs and hydraulic pulse testing and electromagnetic logging provided additional data. One PRB consisted of 40 tonnes of granular iron and was estimated to be an average of 80 mm thick. Based on geophysical imaging, the 100% iron PRB was 15 m long and extended from about 24.5 to 35.5 m depth. The second PRB consisted of a mixture of 5.6 tonnes of well sand and 4.4 tonnes of iron, but was only partially completed. Based on imaging, the sand/iron PRB comprised an area 9 m long extending from about 27 to 34.5 m below the ground surface. The proximity of screened wells, which deviated significantly from vertical toward the PRB alignment, resulted in loss of VHFI control. A sub-horizontal layer of iron formed between the 100% iron PRB and several of the wells. Similarly, piping failure zones formed between the sand/iron PRB and two geophysical wells. Selected groundwater constituents were monitored up- and down-gradient of the two PRBs for 11 months before the PRB emplacement and for 48 months afterwards. Temporary elevated levels of sodium, chloride, and conductance (from the salt tracer), total organic carbon (from the guar) and lowered DO were observed down-gradient of the PRBs. Although the various verification methods confirmed the presence of the 100% iron PRB and its overall continuity, the groundwater data showed no evidence of flow through the granular iron (PCE degradation, elevated pH, dissolved oxygen removal and reducing conditions). This suggests that the groundwater flows around the 100% iron PRB. It is possible that the guar used for the VHFI remained cross-linked, creating a low-permeability barrier. In contrast, the partially completed sand/iron wall did affect the groundwater chemistry in several down-gradient wells. Reducing conditions, zero DO, high pH, and high levels of dissolved iron were noted. A reduction in PCE concentrations and formation of degradation products were observed. (Abstract shortened by UMI.)

  15. Geophysical Monitoring of Two types of Subsurface Injection

    EPA Science Inventory

    Nano-scale particles of zero-valent iron (ZVI) were injected into the subsurface at the 100-D area of the DOE Hanford facility. The intent of this iron injection was to repair a gap in the existing in-situ redox manipulation barrier located at the site. A number of geophysical me...

  16. PLANT MULCH TO TREAT TCE IN GROUND WATER IN A PRB

    EPA Science Inventory

    In the past ten years, passive reactive barriers (PRBs) have found widespread application to treat chlorinated solvent contamination in ground water. The traditional PRB commonly uses granular zero-valent iron and/or iron alloys as filling materials for treatment of chlorinated ...

  17. EFFECTIVE REMOVAL OF TCE IN A LABORATORY MODEL OF A PRB CONSTRUCTED WITH PLANT MULCH

    EPA Science Inventory

    In the past ten years, passive reactive barriers (PRBs) have found widespread application to treat chlorinated solvent contamination in ground water. The traditional PRB commonly uses granular zero-valent iron and/or iron alloys as filling materials for treatment of chlorinated ...

  18. PLANT MULCH TO TREAT TCE IN GROUND WATER IN A PRB (ABSTRACT ONLY)

    EPA Science Inventory

    In the past ten years, passive reactive barriers (PRBs) have found widespread application to treat chlorinated solvent contamination in ground water. The traditional PRB commonly uses granular zero-valent iron and/or iron alloys as filling materials for treatment of chlorinated ...

  19. Advanced hydraulic fracturing methods to create in situ reactive barriers

    SciTech Connect

    Murdoch, L. |; Siegrist, B.; Meiggs, T.

    1997-12-31

    This article describes the use of hydraulic fracturing to increase permeability in geologic formations where in-situ remedial action of contaminant plumes will be performed. Several in-situ treatment strategies are discussed including the use of hydraulic fracturing to create in situ redox zones for treatment of organics and inorganics. Hydraulic fracturing methods offer a mechanism for the in-situ treatment of gently dipping layers of reactive compounds. Specialized methods using real-time monitoring and a high-energy jet during fracturing allow the form of the fracture to be influenced, such as creation of assymmetric fractures beneath potential sources (i.e. tanks, pits, buildings) that should not be penetrated by boring. Some examples of field applications of this technique such as creating fractures filled with zero-valent iron to reductively dechlorinate halogenated hydrocarbons, and the use of granular activated carbon to adsorb compounds are discussed.

  20. Implementation of fluidized granulated iron reactors in a chromate remediation process.

    PubMed

    Mller, 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

  1. Development of iron-based reactive barrier technologies for remediation of chlorinated organic contaminants in groundwater

    SciTech Connect

    Gillham, R.W.

    1998-07-01

    Granular iron was not recognized as an effective reductant for promoting the dechlorination of halocarbons in aqueous solution until the late 1980s. Furthermore, the suggestion that granular iron be used, for in situ remediation of groundwater containing halocarbons was initially met with a high degree of skepticism. In the intervening years, the use of granular iron for groundwater remediation has emerged as a new and significant environmental technology. This paper outlines some of the major contributions that have led to the growing scientific and market acceptance of the technology.

  2. Impact of microbial activities on the mineralogy and performance of column-scale permeable reactive iron barriers operated under two different redox conditions.

    PubMed

    Van Nooten, Thomas; Lieben, François; Dries, Jan; Pirard, Eric; Springael, Dirk; Bastiaens, Leen

    2007-08-15

    The present study focuses on the impact of microbial activities on the performance of various long-term operated laboratory-scale permeable reactive barriers. The barriers contained both aquifer and Fe0 compartments and had received either sulfate or iron(III)-EDTA to promote sulfate-reducing and iron(III)-reducing bacteria, respectively. After dismantlement of the compartments after almost 3 years of operation, DNA-based PCR-DGGE analysis revealed the presence of methanogenic, sulfate-reducing, metal-reducing, and denitrifying bacteria within as well as up- and downgradient of the Fe0 matrix. Under all imposed conditions, the main secondary phases were vivianite, siderite, ferrous hydroxy carbonate, and carbonate green rust as found by scanning electron microscopy (SEM) combined with energy dispersive X-ray analysis (EDX), and X-ray diffraction (XRD). Under sulfate-reduction promoting conditions, iron sulfides were formed in addition, resulting in 7 and 10 times higher degradation rates for PCE and TCE, respectively, compared to unreacted iron. These results indicate that the presence of sulfate-reducing bacteria in or around iron barriers and the subsequent formation of iron sulfides might increase the barrier reactivity. PMID:17874779

  3. Iron

    MedlinePLUS

    ... deficiency anemia. Causes of low iron levels include blood loss, poor diet, or an inability to absorb enough iron from foods. People at higher risk of having too little iron are young ... to build up in the body. Centers for Disease Control and Prevention

  4. 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...

  5. 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 agricultural drainage water filter treatment systems, particularly when nitrate and phosphate pollution are major environmental concerns.

  6. Divalent metal transporter 1 (DMT1) in the brain: implications for a role in iron transport at the blood-brain barrier, and neuronal and glial pathology

    PubMed Central

    Skjrringe, Tina; Burkhart, Annette; Johnsen, Kasper Bendix; Moos, Torben

    2015-01-01

    Iron is required in a variety of essential processes in the body. In this review, we focus on iron transport in the brain and the role of the divalent metal transporter 1 (DMT1) vital for iron uptake in most cells. DMT1 locates to cellular membranes and endosomal membranes, where it is a key player in non-transferrin bound iron uptake and transferrin-bound iron uptake, respectively. Four isoforms of DMT1 exist, and their respective characteristics involve a complex cell-specific regulatory machinery all controlling iron transport across these membranes. This complexity reflects the fine balance required in iron homeostasis, as this metal is indispensable in many cell functions but highly toxic when appearing in excess. DMT1 expression in the brain is prominent in neurons. Of serious dispute is the expression of DMT1 in non-neuronal cells. Recent studies imply that DMT1 does exist in endosomes of brain capillary endothelial cells denoting the blood-brain barrier. This supports existing evidence that iron uptake at the BBB occurs by means of transferrin-receptor mediated endocytosis followed by detachment of iron from transferrin inside the acidic compartment of the endosome and DMT1-mediated pumping iron into the cytosol. The subsequent iron transport across the abluminal membrane into the brain likely occurs by ferroportin. The virtual absent expression of transferrin receptors and DMT1 in glial cells, i.e., astrocytes, microglia and oligodendrocytes, suggest that the steady state uptake of iron in glia is much lower than in neurons and/or other mechanisms for iron uptake in these cell types prevail. PMID:26106291

  7. THE APPLICATION OF PRB TECHNOLOGY AT TWO SITES: LESSONS LEARNED AFTER 7 YEARS OF PERFORMANCE MONITORING

    EPA Science Inventory

    In June of 1996, a 46 m long, 7.3 m deep, and 0.6 m wide permeable reactive barrier (continuous wall configuration) of zero-valent iron was installed at the USCG-SC site. The reactive wall was designed to remediate hexavalent chromium-contaminated groundwater, in addition to tre...

  8. TREATMENT OF ARSENIC AND METALS IN GROUND WATER USING A COMPOST-ZVI PRB

    EPA Science Inventory

    A pilot permeable reactive barrier (PRB) consisting of a mixture of leaf compost, zero-valent iron (ZVI), limestone and pea gravel was installed at a former phosphate fertilizer manufacturing facility in Charleston, S.C. in September 2002. The PRB is designed to treat arsenic an...

  9. GROUND WATER ARSENIC AND METALS TREATMENT USING A COMBINATION COMPOST-ZVI PRB

    EPA Science Inventory

    A pilot permeable reactive barrier (PRB) consisting of a mixture of leaf compost, zero-valent iron (ZVI), limestone and pea gravel was installed at a former phosphate fertilizer manufacturing facility in Charleston, S.C. in September 2002. The PRB is designed to treat arsenic an...

  10. Treatment of Arsenic, Heavy Metals, and Acidity Using a Mixed ZVI-Compost PRB

    EPA Science Inventory

    A 30-month performance evaluation of a pilot permeable reactive barrier (PRB) consisting of a mixture of leaf compost, zero-valent iron (ZVI), limestone and pea gravel installed at a former phosphate fertilizer manufacturing facility was conducted. The PRB is designed to remove ...

  11. GROUND WATER ARSENIC AND METALS TREATMENT USING A COMBINATION COMPOST-ZVI PRB (ABSTRACT ONLY)

    EPA Science Inventory

    A pilot permeable reactive barrier (PRB) consisting of a mixture of leaf compost, zero-valent iron (ZVI), limestone and pea gravel was installed at a former phosphate fertilizer manufacturing facility in Charleston, S.C. in September 2002. The PRB is designed to treat arsenic an...

  12. TREATMENT OF ARSENIC AND METALS IN GROUND WATER USING A COMPOST/ZVI PRB

    EPA Science Inventory

    A pilot permeable reactive barrier (PRB) consisting of a mixture of 30% yard waste compost, 20% zero-valent iron (ZVI), 5% limestone and 45% pea gravel by volume was installed at a former phosphate fertilizer manufacturing facility in Charleston, S.C. in September 2002. The pilo...

  13. Magnetic resonance imaging of post-ischemic blood-brain barrier damage with PEGylated iron oxide nanoparticles

    NASA Astrophysics Data System (ADS)

    Liu, Dong-Fang; Qian, Cheng; An, Yan-Li; Chang, Di; Ju, Sheng-Hong; Teng, Gao-Jun

    2014-11-01

    Blood-brain barrier (BBB) damage during ischemia may induce devastating consequences like cerebral edema and hemorrhagic transformation. This study presents a novel strategy for dynamically imaging of BBB damage with PEGylated supermagnetic iron oxide nanoparticles (SPIONs) as contrast agents. The employment of SPIONs as contrast agents made it possible to dynamically image the BBB permeability alterations and ischemic lesions simultaneously with T2-weighted MRI, and the monitoring could last up to 24 h with a single administration of PEGylated SPIONs in vivo. The ability of the PEGylated SPIONs to highlight BBB damage by MRI was demonstrated by the colocalization of PEGylated SPIONs with Gd-DTPA after intravenous injection of SPION-PEG/Gd-DTPA into a mouse. The immunohistochemical staining also confirmed the leakage of SPION-PEG from cerebral vessels into parenchyma. This study provides a novel and convenient route for imaging BBB alteration in the experimental ischemic stroke model.

  14. REMOVAL OF ADDED NITRATE IN THE SINGLE, BINARY, AND TERNARY SYSTEMS OF COTTON BURR COMPOST, ZEROVALENT IRON, AND SEDIMENT: IMPLICATIONS FOR GROUNDWATER NITRATE REMEDIATION USING PERMEABLE REACTIVE BARRIERS

    EPA Science Inventory

    Recent research has shown that carbonaceous solid materials and zerovalent iron (Fe0) may potentially be used as media in permeable reactive barriers (PRBs) to degrade groundwater nitrate via heterotrophic denitrification in the solid carbon system, and via abiotic reduction and ...

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

    EPA Science Inventory

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

  16. Overview on backfill materials and permeable reactive barriers for nuclear waste disposal facilities.

    SciTech Connect

    Moore, Robert Charles; Hasan, Ahmed Ali Mohamed; Holt, Kathleen Caroline; Hasan, Mahmoud A.

    2003-10-01

    A great deal of money and effort has been spent on environmental restoration during the past several decades. Significant progress has been made on improving air quality, cleaning up and preventing leaching from dumps and landfills, and improving surface water quality. However, significant challenges still exist in all of these areas. Among the more difficult and expensive environmental problems, and often the primary factor limiting closure of contaminated sites following surface restoration, is contamination of ground water. The most common technology used for remediating ground water is surface treatment where the water is pumped to the surface, treated and pumped back into the ground or released at a nearby river or lake. Although still useful for certain remediation scenarios, the limitations of pump-and-treat technologies have recently been recognized, along with the need for innovative solutions to ground-water contamination. Even with the current challenges we face there is a strong need to create geological repository systems for dispose of radioactive wastes containing long-lived radionuclides. The potential contamination of groundwater is a major factor in selection of a radioactive waste disposal site, design of the facility, future scenarios such as human intrusion into the repository and possible need for retrieving the radioactive material, and the use of backfills designed to keep the radionuclides immobile. One of the most promising technologies for remediation of contaminated sites and design of radioactive waste repositories is the use of permeable reactive barriers (PRBs). PRBs are constructed of reactive material(s) to intercept and remove the radionuclides from the water and decontaminate the plumes in situ. The concept of PRBs is relatively simple. The reactive material(s) is placed in the subsurface between the waste or contaminated area and the groundwater. Reactive materials used thus far in practice and research include zero valent iron, hydroxyapatite, magnesium oxide, and others. As the contaminant moves through the reactive material, the contaminant is either sorbed by the reactive material or chemically reacts with the material to form a less harmful substance. Because of the high risk associated with failure of a geological repository for nuclear waste, most nations favor a near-field multibarrier engineered system using backfill materials to prevent release of radionuclides into the surrounding groundwater.

  17. Iron

    MedlinePLUS

    ... that contain vitamin C, like citrus fruits, strawberries, sweet peppers, tomatoes, and broccoli. What kinds of iron ... tiredness and lack of energy, GI upset, poor memory and concentration, and less ability to fight off ...

  18. 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

  19. Performance of a zerovalent iron reactive barrier for the treatment of arsenic in groundwater: Part 2. Geochemical modeling and solid phase studies

    SciTech Connect

    Beak, Douglas G.; Wilkin, Richard T.

    2009-06-12

    Arsenic uptake processes were evaluated in a zerovalent iron reactive barrier installed at a lead smelting facility using geochemical modeling, solid-phase analysis, and X-ray absorption spectroscopy techniques. Aqueous speciation of arsenic is expected to play a key role in directing arsenic uptake processes. Geochemical modeling reveals contrasting pH-dependencies for As(III) and As(V) precipitation. At the moderately alkaline pH conditions typically encountered in zerovalent iron reactive barriers, As(III) is unlikely to precipitate as an oxide or a sulfide phase. Conversely, increasing pH is expected to drive precipitation of metal arsenates including ferrous arsenate. Bacterially mediated sulfate reduction plays an important role in field installations of granular iron. Neoformed iron sulfides provide surfaces for adsorption of oxyanion and thioarsenic species of As(III) and As(V) and are expected to provide enhanced arsenic removal capacity. X-ray absorption near edge structure (XANES) spectra indicate that arsenic is sequestered in the solid phase as both As(III) and As(V) in coordination environments with O and S. Arsenic removal in the PRB probably results from several pathways, including adsorption to iron oxide and iron sulfide surfaces, and possible precipitation of ferrous arsenate. Corrosion of granular iron appears to result in some As(III) oxidation to As(V) as the proportion of As(V) to As(III) in the solid phase is greater compared to influent groundwater. As(0) was not detected in the PRB materials. These results are broadly comparable to laboratory based studies of arsenic removal by zerovalent iron, but additional complexity is revealed in the field environment, which is largely due to the influence of subsurface microbiota.

  20. 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.

  1. 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

  2. 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.

  3. Corrosion and environmental-mechanical characterization of iron-base nuclear waste package structural barrier materials. Annual report, FY 1984

    SciTech Connect

    Westerman, R.E.; Haberman, J.H.; Pitman, S.G.; Pulsipher, B.A.; Sigalla, L.A.

    1986-03-01

    Disposal of high-level nuclear waste in deep underground repositories may require the development of waste packages that will keep the radioisotopes contained for up to 1000 y. A number of iron-base materials are being considered for the structural barrier members of waste packages. Their uniform and nonuniform (pitting and intergranular) corrosion behavior and their resistance to stress-corrosion cracking in aqueous environments relevant to salt media are under study at Pacific Northwest Laboratory. The purpose of the work is to provide data for a materials degradation model that can ultimately be used to predict the effective lifetime of a waste package overpack in the actual repository environment. The corrosion behavior of the candidate materials was investigated in simulated intrusion brine (essentially NaCl) in flowing autoclave tests at 150/sup 0/C, and in combinations of intrusion/inclusion (high-Mg) brine environments in moist salt tests, also at 150/sup 0/C. Studies utilizing a /sup 60/Co irradiation facility were performed to determine the corrosion resistance of the candidate materials to products of brine radiolysis at dose rates of 2 x 10/sup 3/ and 1 x 10/sup 5/ rad/h and a temperature of 150/sup 0/C. These irradiation-corrosion tests were ''overtests,'' as the irradiation intensities employed were 10 to 1000 times as high as those expected at the surface of a thick-walled waste package. With the exception of the high general corrosion rates found in the tests using moist salt containing high-Mg brines, the ferrous materials exhibited a degree of corrosion resistance that indicates a potentially satisfactory application to waste package structural barrier members in a salt repository environment.

  4. Pulsed Magnetic Field Improves the Transport of Iron Oxide Nanoparticles through Cell Barriers

    PubMed Central

    Min, Kyoung Ah; Shin, Meong Cheol; Yu, Faquan; Yang, Meizhu; David, Allan E.; Yang, Victor C.; Rosania, Gus R.

    2013-01-01

    Understanding how a magnetic field affects the interaction of magnetic nanoparticles (MNPs) with cells is fundamental to any potential downstream applications of MNPs as gene and drug delivery vehicles. Here, we present a quantitative analysis of how a pulsed magnetic field influences the manner in which MNPs interact with, and penetrate across a cell monolayer. Relative to a constant magnetic field, the rate of MNP uptake and transport across cell monolayers was enhanced by a pulsed magnetic field. MNP transport across cells was significantly inhibited at low temperature under both constant and pulsed magnetic field conditions, consistent with an active mechanism (i.e. endocytosis) mediating MNP transport. Microscopic observations and biochemical analysis indicated that, in a constant magnetic field, transport of MNPs across the cells was inhibited due to the formation of large (>2 μm) magnetically-induced MNP aggregates, which exceeded the size of endocytic vesicles. Thus, a pulsed magnetic field enhances the cellular uptake and transport of MNPs across cell barriers relative to a constant magnetic field by promoting accumulation while minimizing magnetically-induced MNP aggregates at the cell surface. PMID:23373613

  5. 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 6nm 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 100mg/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

  6. Influence of dissolved inorganic carbon and calcium on gas formation and accumulation in iron permeable reactive barriers.

    PubMed

    Ruhl, Aki S; Weber, Anne; Jekel, Martin

    2012-11-01

    Uncertainties in long-term reactivity and gas accumulation in Fe(0) permeable reactive barriers still hinder a broad application of this groundwater remediation technology. In this study long-term column experiments were conducted under varying geochemical conditions. Generation of hydrogen by anaerobic corrosion in Fe(0) reactive filters was mainly influenced by the mass flux of dissolved inorganic carbon. Both increased concentrations and volume flows led to a substantial rise in gas generation but only to slight differences of gas accumulation within the pores of the reactive filter. Comparisons of columns with different lengths showed higher averaged corrosion rates in the shorter and lower corrosion rates in the longer columns. Calcium in conjunction with dissolved inorganic carbon formed compact and localized aragonite minerals, while in the absence of calcium chukanovite dominated, which covered and passivated the reactive surface to a higher extent. Magnetite was the major crystalline corrosion product in the absence of carbonate and no decline in long term corrosion rates was observed within up to 700 days of operation. Total gas yields of columns were restricted by passivation and approached a volume of approximately 13.5 mL/g granulated cast iron. PMID:23069647

  7. Influence of dissolved inorganic carbon and calcium on gas formation and accumulation in iron permeable reactive barriers

    NASA Astrophysics Data System (ADS)

    Ruhl, Aki S.; Weber, Anne; Jekel, Martin

    2012-11-01

    Uncertainties in long-term reactivity and gas accumulation in Fe(0) permeable reactive barriers still hinder a broad application of this groundwater remediation technology. In this study long-term column experiments were conducted under varying geochemical conditions. Generation of hydrogen by anaerobic corrosion in Fe(0) reactive filters was mainly influenced by the mass flux of dissolved inorganic carbon. Both increased concentrations and volume flows led to a substantial rise in gas generation but only to slight differences of gas accumulation within the pores of the reactive filter. Comparisons of columns with different lengths showed higher averaged corrosion rates in the shorter and lower corrosion rates in the longer columns. Calcium in conjunction with dissolved inorganic carbon formed compact and localized aragonite minerals, while in the absence of calcium chukanovite dominated, which covered and passivated the reactive surface to a higher extent. Magnetite was the major crystalline corrosion product in the absence of carbonate and no decline in long term corrosion rates was observed within up to 700 days of operation. Total gas yields of columns were restricted by passivation and approached a volume of approximately 13.5 mL/g granulated cast iron.

  8. Corrosion resistance of cast irons and titanium alloys as reference engineered metal barriers for use in basalt geologic storage: a literature assessment

    SciTech Connect

    Charlot, L.A.; Westerman, R.E.

    1981-07-01

    A survey and assessment of the literature on the corrosion resistance of cast irons and low-alloy titanium are presented. Selected engineering properties of cast iron and titanium are briefly described; however, the corrosion resistance of cast iron and titanium in aqueous solutions or in soils and their use in a basalt repository are emphasized. In evaluating the potential use of cast iron and titanium as structural barrier materials for long-lived nuclear waste packages, it is assumed that titanium has the general corrosion resistance to be used in relatively thin cross sections whereas the cost and availability of cast iron allows its use even in very thick cross sections. Based on this assumption, the survey showed that: The uniform corrosion of low-alloy titanium in a basalt environment is expected to be extremely low. A linear extrapolation of general corrosion rates with an added corrosion allowance suggests that a 3.2- to 6.4-mm-thick wall may have a life of 1000 yr. Pitting and crevice corrosion are not likely corrosion modes in basalt ground waters. It is also unlikely that stress corrosion cracking (SCC) will occur in the commercially pure (CP) titanium alloy or in palladiumor molybdenum-alloyed titanium materials. Low-alloy cast irons may be used as barrier metals if the environment surrounding the metal keeps the alloy in the passive range. The solubility of the corrosion product and the semipermeable nature of the oxide film allow significant uniform corrosion over long time periods. A linear extrapolation of high-temperature corrosion rates on carbon steels and corrosion rates of cast irons in soils gives an estimated metal penetration of 51 to 64 mm after 1000 yr. A corrosion allowance of 3 to 5 times that suggests that an acceptable cast iron wall may be from 178 to 305 mm thick. Although they cannot be fully assessed, pitting and crevice corrosion should not affect cast iron due to the ground-water chemistry of basalt.

  9. Efflux of Iron from the Cerebrospinal Fluid to the Blood at the Blood-CSF Barrier: Effect of Manganese Exposure

    PubMed Central

    Wang, Xueqian; Li, G. Jane; Zheng, Wei

    2014-01-01

    The blood-cerebrospinal fluid (CSF) barrier (BCB) resides within the choroid plexus, with the apical side facing the CSF and the basolateral side towards the blood. Previous studies demonstrate that manganese (Mn) exposure in rats disrupts iron (Fe) homeostasis in the blood and CSF. The present study used a primary culture of rat choroidal epithelial cells grown in the two-chamber Transwell system to investigate the transepithelial transport of Fe across the BCB. Free, unbound Fe as [59Fe] was added to the donor chamber and the radioactivity in the acceptor chamber was quantified to determine the direction of Fe fluxes. Under the normal condition, the [59Fe] efflux (from the CSF to the blood) was 128% higher than that of the influx (P < 0.01). Mn exposure significantly increased the efflux rate of [59Fe] (P < 0.01) and the effect was inhibited when the cells were pre-incubated with the antibody against divalent metal transport 1 (DMT1). Moreover, when the siRNA knocked down the cellular DMT1 expression, the elevated Fe uptake caused by Mn exposure in the choroidal epithelial Z310 cells was completely abolished, indicating that Mn may facilitate Fe efflux via a DMT1-mediated transport mechanism. In vivo subchronic exposure to Mn in rats reduced Fe clearance from the CSF, as demonstrated by the ventriculo-cisternal brain perfusion, along with up-regulated mRNAs encoding DMT1 and transferrin receptor (TfR) in the same animals. Taken together, these data suggest that free Fe appears to be favorably transported from the CSF toward the blood by DMT1 and this process can be facilitated by Mn exposure. Enhanced TfR-mediated influx of Fe from the blood and ferroportin-mediated expelling Fe toward the CSF may compromise DMT1-mediated efflux, leading to an increased Fe concentration in the CSF as seen in Mn-exposed animals. PMID:18849539

  10. Remediation of the Highland Drive South Ravine, Port Hope, Ontario: Contaminated Groundwater Discharge Management Using Permeable Reactive Barriers and Contaminated Sediment Removal - 13447

    SciTech Connect

    Smyth, David; Roos, Gillian; Ferguson Jones, Andrea; Case, Glenn; Yule, Adam

    2013-07-01

    The Highland Drive South Ravine (HDSR) is the discharge area for groundwater originating from the Highland Drive Landfill, the Pine Street North Extension (PSNE) roadbed parts of the Highland Drive roadbed and the PSNE Consolidation Site that contain historical low-level radioactive waste (LLRW). The contaminant plume from these LLRW sites contains elevated concentrations of uranium and arsenic and discharges with groundwater to shallow soils in a wet discharge area within the ravine, and directly to Hunt's Pond and Highland Drive South Creek, which are immediately to the south of the wet discharge area. Remediation and environmental management plans for HDSR have been developed within the framework of the Port Hope Project and the Port Hope Area Initiative. The LLRW sites will be fully remediated by excavation and relocation to a new Long-Term Waste Management Facility (LTWMF) as part of the Port Hope Project. It is projected, however, that the groundwater contaminant plume between the remediated LLRW sites and HDSR will persist for several hundreds of years. At the HDSR, sediment remediation within Hunt's Ponds and Highland Drive South Creek, excavation of the existing and placement of clean fill will be undertaken to remove current accumulations of solid-phase uranium and arsenic associated with the upper 0.75 m of soil in the wet discharge area, and permeable reactive barriers (PRBs) will be used for in situ treatment of contaminated groundwater to prevent the ongoing discharge of uranium and arsenic to the area in HDSR where shallow soil excavation and replacement has been undertaken. Bench-scale testing using groundwater from HDSR has confirmed excellent treatment characteristics for both uranium and arsenic using permeable reactive mixtures containing granular zero-valent iron (ZVI). A sequence of three PRBs containing ZVI and sand in backfilled trenches has been designed to intercept the groundwater flow system prior to its discharge to the ground surface and the creek and ponds in the HDSR. The first of the PRBs will be installed immediately up-gradient of the wet discharge area approximately 50 m from the creek, the other two will be installed across the area of shallow soil replacement, and all will extend from ground surface to the base of the water table aquifer through which the impacted groundwater flows. The PRBs have been designed to provide the removal of uranium and arsenic for decades, although the capacity of the treatment mixture for contaminant removal suggests that a longer period of treatment may be feasible. The environmental management plan includes an allowance for on-going monitoring, and replacement of a PRB(s) as might be required. (authors)

  11. 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.

  12. Investigating the potential for long-term permeable reactive barrier (PRB) monitoring from the electrical signatures associated with the reduction in reactive iron performance

    SciTech Connect

    Slater, Lee

    2004-06-15

    The objective of this project is to quantify the ability of the electrical induced polarization (IP) method to noninvasively monitor the reduction in reactive iron performance that is known to reduce the effectiveness of the permeable reactive barrier (PRB) with time. The primary scientific goals include: (A) fundamental laboratory studies to evaluate the sensitivity of the IP method to: Fe0 total surface area Fe0 surface chemistry physical/chemical changes to the Fe0 surface resulting from oxidation and precipitation; (B) monitoring of the electrical tomographic response of the Kansas City PRB over a three-year period and assessment, via correlation with aqueous geochemical data and extracted iron cores, of whether electrical signatures associated with reduced PRB performance are resolvable in field studies; (C) optimization of a three-dimensional tomographic imaging algorithm for application to highly conductive, high electrical contrast environments as represented by a PRB.

  13. LONG-TERM GEOCHEMICAL BEHAVIOR OF A ZEROVALENT IRON PERMEABLE REACTIVE BARRIER FOR THE TREATMENT OF HEXAVALENT CHROMIUM IN GROUNDWATER

    EPA Science Inventory

    Passive, in-situ reactive barriers have proven to be viable, cost-effective systems for the remediation of Cr-contaminated groundwater at some sites. Permeable reactive barriers (PRBs) are installed in the flow-p