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1

Microbiological characteristics in a zero-valent iron reactive barrier  

SciTech Connect

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

Gu, Baohua [ORNL; Watson, David B [ORNL; Wu, Liyou [University of Oklahoma, Norman; Phillips, Debra Helen [ORNL; White, David C. [University of Tennessee; Zhou, Jizhong [ORNL

2002-01-01

2

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

Microsoft Academic Search

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

Korte

2001-01-01

3

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

Microsoft Academic Search

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

R. L. Johnson; R. B. Thoms; R. O’Brien Johnson; J. T. Nurmi; Paul G. Tratnyek

2008-01-01

4

Heavy metals removal and hydraulic performance in zero-valent iron\\/pumice permeable reactive barriers  

Microsoft Academic Search

Long-term behaviour is a major issue related to the use of zero-valent iron (ZVI) in permeable reactive barriers for groundwater remediation; in fact, in several published cases the hydraulic conductivity and removal efficiency were progressively reduced during operation, potentially compromising the functionality of the barrier. To solve this problem, the use of granular mixtures of ZVI and natural pumice has

Nicola Moraci; Paolo S. Calabrò

2010-01-01

5

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

Microsoft Academic Search

Permeable reactive barriers (PRBs) of zero-valent iron (Fe°) are increasingly being used to remediate contaminated ground water. Corrosion of Fe° filings and the formation of precipitates can occur when the PRB material comes in contact with ground water and may reduce the lifespan and effectiveness of the barrier. At present, there are no routine procedures for preparing and analyzing the

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

2003-01-01

6

Field Evidence for Flow Reduction through a Zero-Valent Iron Permeable Reactive Barrier  

Microsoft Academic Search

The combination of detailed multilevel ground water geochemistry samples, a natural-gradient tracer test, minislug tests, and a numerical flow and transport model was used to examine flow through a zero-valent iron permeable reactive barrier (PRB) installed to remove explosives from ground water. After 20 months of operation, the PRB continued to completely re- move explosives from the ground water flowing

R. L. Johnson; R. B. Thoms; R. O’Brien Johnson; T. Krug

2008-01-01

7

Review of Zero Valent Iron and Apatite as reactive materials for Permeable Reactive Barrier  

Microsoft Academic Search

Permeable reactive barrier (PRB) is a technology developed recently in the last years. It has obtained promising results in the removal of several contaminants present in the groundwater. This Term paper focuses the attention on two reactive materials, Zero valent iron and Apatite, employed in the PRB system, giving an overview of the reactions and types of pollutants treated to

Luca Geranio; Evert Elzinga

8

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

SciTech Connect

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

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

1998-09-01

9

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

Microsoft Academic Search

The impact of microbiological and geochemical processes has been a major concern for the long-term performance of permeable reactive barriers containing zero-valent iron (Fe°). To evaluate potential biogeochemical impacts, laboratory studies were performed over a 5-month period using columns containing a diverse microbial community. The conditions chosen for these experiments were designed to simulate high concentrations of bicarbonate and sulfate

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

1999-01-01

10

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

Microsoft Academic Search

This study simulated benzene and toluene biodegradation down gradient of a zero-valent iron permeable reactive barrier (ZVI PRB) that reduces trichloroethylene (TCE). The effects of elevated pH (10.5) and the presence of a common TCE dechlorination by product [cis-1,2-dichloroethene (cis-1,2-DCE)] on benzene and toluene biodegradation were evaluated in batch experiments. The data suggest that alkaline pH (pH 10.5), often observed

Liang Chen; Fei Liu; YuLong Liu; HongZhong Dong; Patricia J. S. Colberg

2011-01-01

11

Heavy metals removal and hydraulic performance in zero-valent iron/pumice permeable reactive barriers.  

PubMed

Long-term behaviour is a major issue related to the use of zero-valent iron (ZVI) in permeable reactive barriers for groundwater remediation; in fact, in several published cases the hydraulic conductivity and removal efficiency were progressively reduced during operation, potentially compromising the functionality of the barrier. To solve this problem, the use of granular mixtures of ZVI and natural pumice has recently been proposed. This paper reports the results of column tests using aqueous nickel and copper solutions of various concentrations. Three configurations of reactive material (ZVI only, granular mixture of ZVI and pumice, and pumice and ZVI in series) are discussed. The results clearly demonstrate that iron-pumice granular mixtures perform well both in terms of contaminant removal and in maintaining the long-term hydraulic conductivity. Comparison with previous reports concerning copper removal by ZVI/sand mixtures reveals higher performance in the case of ZVI/pumice. PMID:20643500

Moraci, Nicola; Calabrò, Paolo S

2010-11-01

12

Long-term performance evaluation of permeable reactive barrier using zero-valent iron  

NASA Astrophysics Data System (ADS)

Long-term performance of a permeable reactive barrier (PRB) filled with zero-valent iron (ZVI) and crushed stone as reactive media was evaluated by about ten years groundwater monitoring from its installation. After 2619 days (about 7.2 years), increase of chlorinated volatile organic carbons (CVOCs) concentrations in groundwater was observed at down-gradient wells. Reactive media was sampled from the center of PRB at 3158 days (about 8.7 years) to conduct a series of laboratory tests, which examines the dechlorination coefficient and the conditions of iron powder. Test results showed the iron powder from PRB still maintains sufficient dechlorination ability of CVOCs, and the thickness of corrosion material ranges less than 5?m and the most of the metal portion remains. Therefore, it was considered that the PRB preserves its function to reduce CVOCs concentration in groundwater met the Environmental Quality Standards for Groundwater (EQSG) of Japan.

Nakashima, Makoto; Negishi, Masanori

13

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

Microsoft Academic Search

A series of laboratory experiments were performed to elucidate the chromium transformation and precipitation reactions caused by the corrosion of zero-valent iron in water-based systems. Reaction rates were determined for chromate reduction in the presence of different types of iron and in systems with iron mixed with aquifer materials. Various geochemical parameters were measured to confirm the proposed reactions. Laboratory

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

1998-01-01

14

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...

15

Coupling Electrokinetics with Permeable Reactive Barriers of Zero-Valent Iron for Treating a Chromium Contaminated Soil  

Microsoft Academic Search

Electrokinetic (EK) remediation coupled with permeable reactive barriers (PRB) of zero-valent iron (ZVI) was applied for treating a Cr contaminated soil. Results show that loading ZVI-PRBs in different locations of soil column strongly affected the EK performance. Transport of Cr in the soil column was resulted from the balance of its electromigration and electroosmosis (EO). With increasing treatment time, the

Long Cang; Dong-Mei Zhou; Dan-Ya Wu; Akram N. Alshawabkeh

2009-01-01

16

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 ...

17

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

SciTech Connect

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.

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

2008-07-01

18

Immobilization of Arsenic and Manganese in Contaminated Groundwater by Permeable Reactive Barriers Using Zero Valent Iron and Sheep Manure  

Microsoft Academic Search

A permeable reactive barriers (PRBs) column test was carried out to remove arsenic (As) and manganese (Mn) from groundwater using zero valent iron (ZVI), sheep manure, compost and woodchips as reactive materials. Arsenic was mainly immobilized through sorption and co-precipitation with iron-bearing minerals, and also possibly precipitation as FeAsO4. The presence of sulfate-reducing bacteria (SRB) in the inoculated column was

Wahyu Wilopo; Keiko Sasaki; Tsuyoshi Hirajima; Toshiro Yamanaka

2008-01-01

19

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

SciTech Connect

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.

Korte, NE

2001-06-11

20

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

PubMed

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

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

2011-04-15

21

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

SciTech Connect

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

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

2003-03-01

22

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

PubMed

Permeable reactive barriers (PRBs) of zero-valent iron (Fe(0)) are increasingly being used to remediate contaminated ground water. Corrosion of Fe(0) filings and the formation of precipitates can occur when the PRB material comes in contact with ground water and may reduce the lifespan and effectiveness of the barrier. At present, there are no routine procedures for preparing and analyzing the mineral precipitates from Fe(0) PRB material. These procedures are needed because mineralogical composition of corrosion products used to interpret the barrier processes can change with iron oxidation and sample preparation. The objectives of this study were (i) to investigate a method of preparing Fe(0) reactive barrier material for mineralogical analysis by X-ray diffraction (XRD), and (ii) to identify Fe mineral phases and rates of transformations induced by different mineralogical preparation techniques. Materials from an in situ Fe(0) PRB were collected by undisturbed coring and processed for XRD analysis after different times since sampling for three size fractions and by various drying treatments. We found that whole-sample preparation for analysis was necessary because mineral precipitates occurred within the PRB material in different size fractions of the samples. Green rusts quickly disappeared from acetone-dried samples and were not present in air-dried and oven-dried samples. Maghemite/magnetite content increased over time and in oven-dried samples, especially after heating to 105 degrees C. We conclude that care must be taken during sample preparation of Fe(0) PRB material, especially for detection of green rusts, to ensure accurate identification of minerals present within the barrier system. PMID:12931885

Phillips, D H; Gu, B; Watson, D B; Roh, Y

2003-01-01

23

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

SciTech Connect

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

Kwong, S.; Small, J.; Tahar, B. [Nexia Solutions Ltd., Hinton House, Risley, Warrington, WA (United Kingdom)

2007-07-01

24

Chlorine and carbon isotope measurements can help assessing the effectivenes of a zero valent iron barrier  

NASA Astrophysics Data System (ADS)

Chlorinated aliphatic hydrocarbons (CAH's) such as trichloroethene (TCE), cis-dichloroethene (cis-DCE) and vinylchloride (VC) are extensively used in industrial applications. One of the most promising remediation techniques for CAH's in groundwater is their removal via abiotic reductive dechlorination using Zero Valent Iron (ZVI). This is applied for the treatment of contaminated sites by installing permeable reactive barriers (PRB). In this study, isotope fractionation of chlorinated ethylenes in transformation by cast iron has been investigated, because such types of iron are commonly used in PRBs. Batch experiments have been carried out in closed flasks, containing cast iron with aqueous solutions of TCE, cDCE and VC. These substrates and their respective products have been monitored by headspace samplings for their concentration (by GC-FID) and isotope fractionation of carbon and chlorine (by GC-IRMS). A decreasing reactivity trend was observed when compounds contain less chlorine atoms, with differences in rate constants of about one order of magnitude between each of the substances TCE > cDCE > VC. This resulted in the accumulation of products with fewer chlorine atoms. Therefore a similar observation can be expected if degradation in the field is incomplete, for example in the case of aged or improperly designed PRB. Pronounced carbon and chlorine isotope fractionation was measured for each of the compounds, and characteristic dual isotope plots (C, Cl) were obtained for TCE and cDCE. These results may serve as an important reference for the interpretation of isotope data from field sites, since stable isotope fractionation is widely recognized as robust indicator for such pollutant transformations. However, carbon isotope fractionation in a given parent compound may be caused by either abiotic or biotic degradation. In the field, it can therefore be difficult to delineate the contribution of abiotic transformation by PRB in the presence of ongoing biodegradation. This study investigates two different approaches to resolve these concurring modes of transformation: (i) evidence from dual (C, Cl) isotope plots; (ii) evidence from carbon isotope values of degradation products (e.g., cDCE and ethene from TCE, respectively). The comparison of dual isotope patterns for TCE degradation with cast iron and with Geobacter lovleyi exhibited similar slopes for these two types of reaction. This indicates that dual isotope plots may not be able to distinguish biotic and abiotic pathways in this case. However, the information from carbon isotope values in this study confirms earlier results (Elsner et al.), which suggest that isotope values from reaction products can be a expedient way of delineating the occurrence of abiotic trans¬formation, even in the presence of ongoing biodegradation.

Cretnik, S.; Audi, C.; Bernstein, A.; Palau, J.; Soler, A.; Elsner, M.

2012-04-01

25

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

NASA Astrophysics Data System (ADS)

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.

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

2007-12-01

26

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

USGS Publications Warehouse

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.

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

1999-01-01

27

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...

28

Zero-valent iron nanoparticles preparation  

SciTech Connect

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.

Oropeza, S. [Instituto Politécnico Nacional, ESIQIE, UPALM, Edificio Z-6, Primer Piso, C.P. 07738, Col. San Pedro Zacatenco, México D.F. (Mexico)] [Instituto Politécnico Nacional, ESIQIE, UPALM, Edificio Z-6, Primer Piso, C.P. 07738, Col. San Pedro Zacatenco, México D.F. (Mexico); Corea, M., E-mail: mcoreat@yahoo.com.mx [Instituto Politécnico Nacional, ESIQIE, UPALM, Edificio Z-6, Primer Piso, C.P. 07738, Col. San Pedro Zacatenco, México D.F. (Mexico); Gómez-Yáñez, C. [Instituto Politécnico Nacional, ESIQIE, UPALM, Edificio Z-6, Primer Piso, C.P. 07738, Col. San Pedro Zacatenco, México D.F. (Mexico)] [Instituto Politécnico Nacional, ESIQIE, UPALM, Edificio Z-6, Primer Piso, C.P. 07738, Col. San Pedro Zacatenco, México D.F. (Mexico); Cruz-Rivera, J.J. [Universidad Autónoma de San Luis Potosí, Instituto de Metalurgia, Sierra Leona 550, San Luis Potosí, C.P. 78210 (Mexico)] [Universidad Autónoma de San Luis Potosí, Instituto de Metalurgia, Sierra Leona 550, San Luis Potosí, C.P. 78210 (Mexico); Navarro-Clemente, M.E., E-mail: mnavarroc@ipn.mx [Instituto Politécnico Nacional, ESIQIE, UPALM, Edificio Z-6, Primer Piso, C.P. 07738, Col. San Pedro Zacatenco, México D.F. (Mexico)

2012-06-15

29

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

PubMed

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

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

2003-01-01

30

Performance evaluation of a zero-valent iron reactive barrier: mineralogical characteristics  

SciTech Connect

There is a limited amount of information about the effects of mineral precipitates and corrosion on the lifespan and long-term performance of in situ Fe{sup 0} reactive barriers. The objectives of this paper are (1) to investigate mineral precipitates through an in situ permeable Fe{sup 0} reactive barrier and (2) to examine the cementation and corrosion of Fe{sup 0} filings in order to estimate the lifespan of this barrier. This field scale barrier (225-ft long x 2-ft wide x 31-ft deep) has been installed in order to remove uranium from contaminated groundwater at the Y-12 plant site, Oak Ridge, TN. According to XRD and SEM-EDX analysis of core samples recovered from the Fe{sup 0} portion of the barrier, iron oxyhydroxides were found throughout, while aragonite, siderite, and FeS occurred predominantly in the shallow portion. Additionally, aragonite and FeS were present in up-gradient deeper zone where groundwater first enters the Fe{sup 0} section of the barrier. After 15 months in the barrier, most of the Fe{sup 0} filings in the core samples were loose, and a little corrosion of Fe{sup 0} filings was observed in most of the barrier. However, larger amounts of corrosion (10-150 {micro}m thick corrosion rinds) occurred on cemented iron particles where groundwater first enters the barrier. Bicarbonate/carbonate concentrations were high in this section of the barrier. Byproducts of this corrosion, iron oxyhydroxides, were the primary binding material in the cementation. Also, aragonite acted as a binding material to a lesser extent, while amorphous FeS occurred as coatings and infilings. Thin corrosion rinds (2-50 {micro}m thick) were also found on the uncemented individual Fe{sup 0} filings in the same area of the cementation. If corrosion continues, the estimated lifespan of Fe{sup 0} filings in the more corroded sections is 5 to 10 years, while the Fe{sup 0} filings in the rest of the barrier perhaps would last longer than 15 years. The mineral precipitates on the Fe{sup 0} filing surfaces may hinder this corrosion but they may also decrease reactive surfaces. This research shows that precipitation will vary across a single reactive barrier and that greater corrosion and subsequent cementation of the filings may occur where groundwater first enters the Fe{sup 0} section of the barrier.

Phillips, Debra Helen [ORNL; Gu, Baohua [ORNL; Watson, David B [ORNL; Roh, Yul [ORNL; Liang, Liyuan [ORNL; Lee, S. Y. [University of Tennessee, Knoxville (UTK)

2000-08-01

31

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

SciTech Connect

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.

Newcomer, Darrell R.

2009-02-09

32

Long-Term Performance of Zero-Valent Iron Permeable Reactive Barriers: A Critical Review  

Microsoft Academic Search

Permeable reactive barriers (PRBs) have shown great promise as an alternative to pump and treat for the remediation of groundwater containing a wide array of contaminants including organics, metals, and ra- dionuclides. Analyses to date have focused on individual case studies, rather than considering broad per- formance issues. In response to this need, this study analyzed data from field installations

Andrew D. Henderson; Avery H. Demond

2007-01-01

33

Arsenic(V) removal from groundwater using nano scale zero-valent iron as a colloidal reactive barrier material.  

PubMed

The removal of As(V), one of the most poisonous groundwater pollutants, by synthetic nanoscale zero-valent iron (NZVI) was studied. Batch experiments were performed to investigate the influence of pH, adsorption kinetics, sorption mechanism, and anionic effects. Field emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HR-TEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and Mossbauer spectroscopy were used to characterize the particle size, surface morphology, and corrosion layer formation on pristine NZVI and As(V)-treated NZVI. The HR-TEM study of pristine NZVI showed a core-shell-like structure, where more than 90% of the nanoparticles were under 30 nm in diameter. Mössbauer spectroscopy further confirmed its structure in which 19% were in zero-valent state with a coat of 81% iron oxides. The XRD results showed that As(V)-treated NZVI was gradually converted into magnetite/maghemite corrosion products over 90 days. The XPS study confirmed that 25% As(V) was reduced to As(III) by NZVI after 90 days. As(V) adsorption kinetics were rapid and occurred within minutes following a pseudo-first-order rate expression with observed reaction rate constants (Kobs) of 0.02-0.71 min(-1) at various NZVI concentrations. Laser light scattering analysis confirmed that NZVI-As(V) forms an inner-sphere surface complexation. The effects of competing anions revealed that HCO3-, H4SiO4(0), and H2PO4(2-) are potential interfering agents in the As(V) adsorption reaction. Our results suggest that NZVI is a suitable candidate for As(V) remediation. PMID:16570634

Kanel, Sushil Raj; Greneche, Jean-Mark; Choi, Heechul

2006-03-15

34

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

Microsoft Academic Search

In this study, two mixtures of municipal compost, limestone and, optionally, zero-valent iron were assessed in two column\\u000a experiments on acid mine treatment. The effluent solution was systematically analysed throughout the experiment and precipitates\\u000a from both columns were withdrawn for scanning electron microscopy, energy-dispersive X-ray spectroscopy, X-ray diffractometry\\u000a analysis and, from the column containing zero-valent iron, solid digestion and sequential

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

2010-01-01

35

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 ...

36

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

SciTech Connect

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.

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

2004-03-31

37

Low frequency electrical properties of zero valent iron: Implications for performance monitoring of permeable reactive barriers (PRBs)  

Microsoft Academic Search

The permeable reactive barrier is an in-situ remediation technology for groundwater contaminants. Long term performance monitoring of PRB is critical to the estimation of barrier efficiency. Iron corrosion and mineral precipitation are recognized as the primary causes of barrier performance reduction and can serve as a proper indicator of barrier efficiency. Electrical signature is sensitive to iron corrosion processes. This

Yuxin Wu

2007-01-01

38

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

PubMed

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

Calabrò, P S; Moraci, N; Suraci, P

2012-03-15

39

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

EPA Science Inventory

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

40

Assessment of zero?valent iron as a permeable reactive barrier for long?term removal of arsenic compounds from synthetic water  

Microsoft Academic Search

Zero?valent iron (ZVI) has great potential to be used as a remediation material for the removal of a wide range of pollutants from groundwater. The present study assessed the potential of ZVI for arsenic remediation by investigating (i) the removal kinetics of arsenic by ZVI in a batch reactor and (ii) the longevity of ZVI to remove arsenic in a

Yunho Lee; Jeyong Yoon

2009-01-01

41

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...

42

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...

43

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...

44

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...

45

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...

46

Conceptual analysis of zero-valent iron fracture reactive barriers for remediating a trichloroethylene plume in a chalk aquifer  

Microsoft Academic Search

A novel concept, the Fe0 fracture reactive barrier (Fe0 FRB), is proposed to clean up chlorinated solvent pollution of groundwater in a chalk aquifer. Iron particles, suspended in a viscous biodegradable gel, can be injected into selected fractures to create an extended reactive zone of partly iron-filled fractures. To evaluate the feasibility of Fe0 FRB as a remediation strategy, we

Zuansi Cai; David N. Lerner; Robert G. McLaren; Ryan D. Wilson

2007-01-01

47

Formation of ferrihydrite and associated iron corrosion products in permeable reactive barriers of zero-valent iron.  

PubMed

Ferrihydrite, which is known to form in the presence of oxygen and to be stabilized by the adsorption of Si, PO4 and SO4, is ubiquitous in the fine-grained fractions of permeable reactive barrier (PRB) samples from the U.S. Coast Guard Support Center (Elizabeth City, NC) and the Denver Federal Center (Lakewood, CO) studied by high-resolution transmission electron microscopy and selected area electron diffraction. The concurrent energy-dispersive X-ray data indicate a strong association between ferrihydrite and metals such as Si, Ca, and Cr. Magnetite, green rust 1, aragonite, calcite, mackinawite, greigite and lepidocrocite were also present, indicative of a geochemical environment that is temporally and spatially heterogeneous. Whereas magnetite, which is known to form due to anaerobic Fe0 corrosion, passivates the Fe0 surface, ferrihydrite precipitation occurs away from the immediate Fe0 surface, forming small (<0.1 microm) discrete clusters. Consequently, Fe0-PRBs may remain effective for a longer period of time in slightly oxidized groundwater systems where ferrihydrite formation occurs compared to oxygen-depleted systems where magnetite passivation occurs. The ubiquitous presence of ferrihydrite suggests that the use of Fe0-PRBs may be extended to applications that require contaminant adsorption rather than, or in addition to, redox-promoted contaminant degradation. PMID:12521177

Furukawa, Yoko; Kim, Jin-Wook; Watkins, Janet; Wilkin, Richard T

2002-12-15

48

Formation of ferrihydrite and associated iron corrosion products in permeable reactive barriers of zero-valent iron  

NASA Technical Reports Server (NTRS)

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.

Furukawa, Yoko; Kim, Jin-Wook; Watkins, Janet; Wilkin, Richard T.

2002-01-01

49

Assessment of zero-valent iron as a permeable reactive barrier for long-term removal of arsenic compounds from synthetic water.  

PubMed

Zero-valent iron (ZVI) has great potential to be used as a remediation material for the removal of a wide range of pollutants from groundwater. The present study assessed the potential of ZVI for arsenic remediation by investigating (i) the removal kinetics of arsenic by ZVI in a batch reactor and (ii) the longevity of ZVI to remove arsenic in a flow-through column system which mimics the permeable reactive barrier (PRB) technology. Results of the batch experiments showed an effective removal (99.5%) of arsenic compounds from the synthetic water samples. Based on our kinetic study, the arsenic removals are expected to occur in a timescale of less than a few hours in typical PRB treatment conditions using ZVI (e.g. [ZVI] > 20 g/L and [As] < 1 mg/L). The flow-through columns were continuously operated for 360 days at a flow rate of 2 mL/h. Samples were taken at regular intervals (90, 150, 230 and 360 days) and analysed for total arsenic concentration. The removal rates decreased by (45% in aerobic and 39% in anoxic) after 360 days of operation indicate that the regular replacement of the reactive material would be required for efficient removal of arsenic. PMID:20088207

Lee, Kui-Jae; Lee, Yunho; Yoon, Jeyong; Kamala-Kannan, Seralathan; Park, Seung-Moon; Oh, Byung-Taek

2009-12-01

50

A Comparison Between Field Applications of Nano, Micro, and Millimetric Zero-Valent Iron for the Remediation of Contaminated Aquifers  

Microsoft Academic Search

In the last 10 years, the number of field applications of zero-valent iron differing from permeable reactive barrier has grown\\u000a rapidly and at present are 112. This study analyzes and compares such field applications. By using statistical analysis, especially\\u000a ANOVA and principal component analysis, this study shows that chlorinated solvent contamination can be treated efficiently\\u000a by using zero-valent iron material singly

Silvia Comba; Antonio Di Molfetta; Rajandrea Sethi

2011-01-01

51

Pressurized CO 2\\/zero valent iron system for nitrate removal  

Microsoft Academic Search

A fluidized zero valent iron (ZVI) reactor pressurized by CO2 gas for controlling pH was employed for nitrate reduction. The proposed CO2 pressurized system potentially has advantages of using less CO2 gas and reaching equilibrium pH faster than CO2-bubbled system. However, due to weak acid nature of carbonic acid, system pH gradually increased with increasing oxidation of ZVI and reduction

Chi-Wang Li; Yi-Ming Chen; Wei-Shuen Yen

2007-01-01

52

Potential artifacts in interpretation of differential breakthrough of colloids and dissolved tracers in the context of transport in a zero-valent iron permeable reactive barrier.  

PubMed

Many published studies have used visual comparison of the timing of peak breakthrough of colloids versus conservative dissolved tracers (hereafter referred to as dissolved tracers or tracers) in subsurface media to determine whether they are advected differently, and to elucidate the mechanisms of differential advection. This purely visual approach of determining differential advection may have artifacts, however, due to the attachment of colloids to subsurface media. The attachment of colloids to subsurface media may shift the colloidal peak breakthrough to earlier times, causing an apparent "faster" peak breakthrough of colloids relative to dissolve tracers even though the transport velocities for the colloids and the dissolved tracers may actually be equivalent. In this paper, a peak shift analysis was presented to illustrate the artifacts associated with the purely visual approach in determining differential advection, and to quantify the peak shift due to colloid attachment. This peak shift analysis was described within the context of microsphere and bromide transport within a zero-valent iron (ZVI) permeable reactive barrier (PRB) located in Fry Canyon, Utah. Application of the peak shift analysis to the field microsphere and bromide breakthrough data indicated that differential advection of the microspheres relative to the bromide occurred in the monitoring wells closest to the injection well in the PRB. It was hypothesized that the physical heterogeneity at the grain scale, presumably arising from differences in inter- versus intra-particle porosity, contributed to the differential advection of the microspheres versus the bromide in the PRB. The relative breakthrough (RB) of microspheres at different wells was inversely related to the ionic strength of ground water at these wells, in agreement with numerous studies showing that colloid attachment is directly related to solution ionic strength. PMID:11708449

Zhang, B P; Johnson, W P; Piana, M J; Fuller, C C; Naftz, D L

2001-01-01

53

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

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.

Zhang, P.; Johnson, W.P.; Piana, M.J.; Fuller, C.C.; Naftz, D.L.

2001-01-01

54

Ten year performance evaluation of a field-scale zero-valent iron permeable reactive barrier installed to remediate trichloroethene contaminated groundwater.  

PubMed

The Monkstown zero-valent iron permeable reactive barrier (ZVI PRB), Europe's oldest commercially-installed ZVI PRB, had been treating trichloroethene (TCE) contaminated groundwater for about 10 years on the Nortel Network site in Northern Ireland when cores from the reactive zone were collected in December, 2006. Groundwater data from 2001-2006 indicated that TCE is still being remediated to below detection limits as the contaminated groundwater flows through the PRB. Ca and Fe carbonates, crystalline and amorphous Fe sulfides, and Fe (hydr)oxides have precipitated in the granular ZVI material in the PRB. The greatest variety of minerals is associated with a approximately 1-2 cm thick, slightly cemented crust on top (up-gradient influent entrance) of the ZVI section of the PRB and also with the discontinuous cemented ZVI material ( approximately 23 cm thick) directly below it. The greatest presence of microbial communities also occurred in the up-gradient influent portion of the PRB compared to its down-gradient effluent section, with the latter possibly due to less favorable conditions (i.e., high pH, low oxygen) for microbial growth. The ZVI filings in the down-gradient effluent section of the PRB have a projected life span of >10 years compared with ZVI filings from the continuous to discontinuous cemented up-gradient ZVI section (upper approximately 25 cm) of the PRB, which may have a life span of only approximately 2-5 more years. Supporting Information from applied, multi-tracer testing indicated that restricted groundwater flow is occurring in the upper approximately 25 cm of the ZVI section and preferential pathways have also formed in this PRB over its 10 years of operation. PMID:20420442

Phillips, D H; Van Nooten, T; Bastiaens, L; Russell, M I; Dickson, K; Plant, S; Ahad, J M E; Newton, T; Elliot, T; Kalin, R M

2010-05-15

55

Application of Emulsified Zero-Valent Iron to Marine Environments  

NASA Technical Reports Server (NTRS)

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.

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

2005-01-01

56

Chromate transport through columns packed with surfactant-modified zeolite/zero valent iron pellets  

E-print Network

Chromate transport through columns packed with surfactant-modified zeolite/zero valent iron pellets or treated with the cationic surfactant hexadecyltrimethylammonium (HDTMA), was studied at different flow

Li, Zhaohui

57

Application of Emulsified Zero-Valent Iron to Marine Environments  

NASA Technical Reports Server (NTRS)

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.

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

2006-01-01

58

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

SciTech Connect

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.

Lenly J. Weathers; Lynn E. Katz

2002-05-29

59

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...

60

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

Microsoft Academic Search

Zero-valent iron (ZVI) installed in permeable reactive barriers (PRBs) has been shown to be an effective remediation agent for several contaminants, including arsenic (As), a redox-active oxyanion present in reduced form as arsenite, AsO3(3-), and in oxidized form as arsenate, AsO4(3-). Work performed has shown greater removal of arsenic by iron sulfide (FeS), as mackinawite, than by ZVI under anaerobic

A. D. Henderson; A. H. Demond

2007-01-01

61

Electrokinetics Enhanced Delivery of Nano-scale Zero Valent Iron  

NASA Astrophysics Data System (ADS)

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.

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

2010-12-01

62

Can zero-valent iron nanoparticles remove waterborne estrogens?  

PubMed

Steroidal estrogens are one of the most challenging classes of hazardous contaminants as they can cause adverse effects to biota in extremely low concentrations. They emerge in both waste waters and surface waters serving as a source of drinking water. Environmental Quality Standards for 17?-estradiol (E2) and 17?-ethinylestradiol (EE2), promulgated within the EU Water Framework Directive, are 0.4 and 0.035 ng L(-1), respectively. Because nanoscale zero-valent iron (nZVI) particles have been previously used in numerous remediation technologies and have the advantage of possible magnetic separation, interaction of nZVI with E2 and EE2 in water was investigated to assess the potential role of nZVI in removing steroidal estrogens. A mixture of E2 and EE2 dissolved in water was shaken with varying doses of nZVI for 1-5 h. Concentration-dependent removal of the estrogens was observed but removal did not increase significantly with time. Concentrations of the estrogens were determined by HPLC/MS/MS and a biodetection reporter gene assay. Sorption and nonspecific oxygen-mediated oxidation of estrogens were identified as the most probable removal mechanisms. Two independent experiments confirmed that significant decrease of estrogens concentration is achieved when at least 2 g L(-1) of nZVI is applied. The presented study provides insights into the mechanisms of nZVI interaction with steroidal estrogens under aerobic conditions prevailing in currently applied water treatment technologies. PMID:25567735

Jarošová, Barbora; Filip, Jan; Hilscherová, Klára; Tu?ek, Ji?í; Šimek, Zden?k; Giesy, John P; Zbo?il, Radek; Bláha, Lud?k

2015-03-01

63

Antimicrobial and Genotoxicity Effects of Zero-valent Iron Nanoparticles  

PubMed Central

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

Barzan, Elham; Mehrabian, Sedigheh; Irian, Saeed

2014-01-01

64

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

NASA Astrophysics Data System (ADS)

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

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

2013-12-01

65

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...

66

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...

67

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...

68

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

EPA Science Inventory

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

69

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...

70

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 ...

71

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...

72

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...

73

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...

74

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

PubMed

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. PMID:19342119

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

2009-05-12

75

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

SciTech Connect

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.

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

2009-06-01

76

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

SciTech Connect

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.

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

2011-10-01

77

Heterogeneous reductive dehalogenation of PCB contaminated transformer oil and brominated diphenyl ethers with zero valent iron.  

PubMed

Reductive dechlorination and debromination of halogenated biphenyls (PCBs) and diphenyl ethers (PBDEs) occurs efficiently at moderately elevated temperatures (350-600 °C) with zero valent iron (iron powder) in a nitrogen atmosphere. The proton donors tested were waste transformer oil, iso-octane, and n-decane. Observation of production of biphenyl and diphenyl ether and their condensation products indicates that the reaction is not simple pyrolysis, but a reduction. No halogenated organic products are observed. PMID:22560182

Habekost, A; Aristov, N

2012-09-01

78

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

Microsoft Academic Search

This study was undertaken to determine the effectiveness of zero-valent iron (Fe°) and several adsorbent materials in removing uranium (U) from contaminated groundwater and to investigate the rates and mechanisms that are involved in the reactions. Fe° filings were used as reductants, and the adsorbents included peat materials, iron oxides, and a carbon-based sorbent (Cercona Bone-Char). Results indicate that Fe°

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

1998-01-01

79

Olive mill wastewater degradation by Fenton oxidation with zero-valent iron and hydrogen peroxide  

Microsoft Academic Search

The degradation of olive mill wastewater (OMW) with hydroxyl radicals generated from zero-valent iron and hydrogen peroxide has been investigated by means of chemical oxygen demand (COD) and phenolic compounds analyses. The effects of the H2O2 dose, the pH and the organic matter concentration have been studied. The optimal experimental conditions were found to have continuous presence of iron metal,

Monem Kallel; Chokri Belaid; Rachdi Boussahel; Mohamed Ksibi; Antoine Montiel; Boubaker Elleuch

2009-01-01

80

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...

81

Toxicity of nano-zero valent iron to freshwater and marine organisms.  

PubMed

We tested whether three commercial forms (uncoated, organic coating, and iron oxide coating) of nano zero-valent iron (nZVI) are toxic to freshwater and marine organisms, specifically three species of marine phytoplankton, one species of freshwater phytoplankton, and a freshwater zooplankton species (Daphnia magna), because these organisms may be exposed downstream of where nZVI is applied to remediate polluted soil. The aggregation and reactivity of the three types of nZVI varied considerably, which was reflected in their toxicity. Since levels of Fe(2+) and Fe(3+) increase as the nZVI react, we also evaluated their toxicity independently. All four phytoplankton species displayed decreasing population growth rates, and Daphnia magna showed increasing mortality, in response to increasing levels of nZVI, and to a lesser degree with increasing Fe(2+) and Fe(3+). All forms of nZVI aggregated in soil and water, especially in the presence of a high concentration of calcium ions in groundwater, thus reducing their transports through the environment. However, uncoated nZVI aggregated extremely rapidly, thus vastly reducing the probability of environmental transport and potential for toxicity. This information can be used to design a risk management strategy to arrest the transport of injected nZVI beyond the intended remediation area, by injecting inert calcium salts as a barrier to transport. PMID:22952836

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

2012-01-01

82

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

PubMed Central

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

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

2012-01-01

83

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

PubMed

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

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

2014-02-28

84

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 ...

85

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...

86

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

Microsoft Academic Search

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

Richard T. Wilkin; Mary S. McNeil

2003-01-01

87

The impact of zero-valent iron nanoparticles on a river water bacterial community  

Microsoft Academic Search

Zero-valent iron (ZVI) nanoparticles are of interest because of their many potential biomedical and environmental applications. However, these particles have recently been reported to be cytotoxic to bacterial cells. The overall objective of this study was to determine the impact of 100mg\\/L ZVI nanoparticles on the diversity and structure of an indigenous river water bacterial community. Response during exposure for

Robert J. Barnes; Christopher J. van der Gast; Olga Riba; Laura E. Lehtovirta; James I. Prosser; Peter J. Dobson; Ian P. Thompson

2010-01-01

88

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

Microsoft Academic Search

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

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

2009-01-01

89

Effect of Zero-Valent Iron Application on Cadmium Uptake in Rice Plants Grown in Cadmium-Contaminated Soils  

Microsoft Academic Search

Cadmium (Cd) contamination in soils is a serious problem for crop production in the world. Zero-valent iron [Fe (0)] is a reactive material with reducing power capable of stabilizing toxic elements in a solution. In the present study, we examined the effect of zero-valent iron [Fe (0)] application on Cd accumulation in rice plants growing in Cd-contaminated paddy soils. The

Toshihiro Watanabe; Yasutoshi Murata; Takashi Nakamura; Yuki Sakai; Mitsuru Osaki

2009-01-01

90

Performance of a field-scale permeable reactive barrier based on organic substrate and zero-valent iron for in situ remediation of acid mine drainage.  

PubMed

A permeable reactive barrier (PRB) was installed in Aznalcóllar (Spain) in order to rehabilitate the Agrio aquifer groundwater severely contaminated with acid mine drainage after a serious mining accident. The filling material of the PRB consisted of a mixture of calcite, vegetal compost and, locally, Fe(0) and sewage sludge. Among the successes of the PRB are the continuous neutralisation of pH and the removal of metals from groundwater within the PRB (removals of >95%). Among the shortcomings are the improper PRB design due to the complexity of the internal structure of the Agrio alluvial deposits (which resulted in an inefficient capture of the contaminated plume), the poor degradability of the compost used and the short residence time within the PRB (which hindered a complete sulphate reduction), the clogging of a section of the PRB and the heterogeneities of the filling material (which resulted in preferential flows within the PRB). Undoubtedly, it is only through accumulated experience at field-scale systems that the potentials and limits of the PRB technology can be determined. PMID:23361181

Gibert, Oriol; Cortina, José Luis; de Pablo, Joan; Ayora, Carlos

2013-11-01

91

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

SciTech Connect

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

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

2007-02-15

92

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

PubMed

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

Kim, Heonki; Yang, Haewon; Kim, Juyoung

2014-01-01

93

Zero valent iron remediation of a mixed brominated ethene contaminated groundwater.  

PubMed

The suitability of a granulated zero valent iron (ZVI) permeable reactive barrier (PRB) remediation strategy was investigated for tribromoethene (TriBE), cis-1,2-dibromoethene (c-DBE), trans-1,2-dibromoethene (t-DBE) and vinyl bromide (VB), via batch and large-scale column experiments that were subsequently analysed by reactive transport modelling. The brominated ethenes in both batch and large-scale column experiments showed rapid (compared to controls and natural attenuation) degradation in the presence of ZVI. In the large-scale column experiment, degradation half-lives were 0.35 days for TriBE, 0.50 days for c-DBE, 0.31 days for t-DBE and 0.40 days for VB, under site groundwater flow conditions, resulting in removal of brominated ethenes within the first 0.2 m of a 1.0 m thick ZVI layer, indicating that a PRB groundwater remediation strategy using ZVI could be used successfully. In the model simulations of the ZVI induced brominated ethene degradation, assuming a dominant reductive beta-elimination pathway via bromoacetylene and acetylene production, simulated organic compound concentrations corresponded well with both batch and large-scale column experimental data. Changes of inorganic reactants were also well captured by the simulations. The similar ZVI induced degradation pathway of TriBE and TCE suggests that outcomes from research on ZVI induced TCE remediation could also be applied to TriBE remediation. PMID:18990465

Cohen, Elizabeth L; Patterson, Bradley M; McKinley, Allan J; Prommer, Henning

2009-01-26

94

Effect of common ions on nitrate removal by zero-valent iron from alkaline soil.  

PubMed

Zero-valent iron (Fe(0))-based permeable reactive barrier (PRB) technology has been proved to be effective for soil and groundwater nitrate remediation under acidic or near neutral conditions. But few studies have been reported about it and the effects of coexistent ions under alkaline conditions. In this study, nitrate reduction by Fe(0) was evaluated via batch tests in the presence of alkaline soil and common cation (Fe(2+), Fe(3+) and Cu(2+)) and anion (citrate, oxalate, acetate, SO(4)(2-), PO(4)(3-), Cl(-) and HCO(3)(-)). The results showed that cation significantly enhanced nitrate reduction with an order of Fe(3+)>Fe(2+)>Cu(2+) due to providing Fe(2+) directly or indirectly. Most anions enhanced nitrate reduction, but PO(4)(3-) behaved inhibition. The promotion decreased in the order of citrate>acetate>SO(4)(2-)>Cl(-)?HCO(3)(-)?oxalate?PO(4)(3-). Ammonium was the major final product from nitrate reduction by Fe(0), while a little nitrite accumulated in the beginning of reaction. The nitrogen recovery in liquid and gas phase was only 56-78% after reaction due to ammonium adsorption onto soil. The solution pH and electric conductivity (EC) varied depending on the specific ion added. The results implied that PRB based Fe(0) is a potential approach for in situ remediation of soil and groundwater nitrate contamination in the alkaline conditions. PMID:22795587

Tang, Cilai; Zhang, Zengqiang; Sun, Xining

2012-09-15

95

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

PubMed

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

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

2013-11-01

96

Removal of organic load and phenolic compounds from olive mill wastewater by Fenton oxidation with zero-valent iron  

Microsoft Academic Search

Pre-treatment of olive mill wastewater (OMW) by Fenton Oxidation with zero-valent iron and hydrogen peroxide was investigated to improve phenolic compounds degradation and the chemical oxygen demand (COD) removal. Experimental procedure is performed with diluted OMW with COD 19g\\/L and pH 5.2. The application of zero-valent Fe\\/H2O2 procedure allows high removal efficiency of pollutants from OMW. The optimal experimental conditions

M. Kallel; C. Belaid; T. Mechichi; M. Ksibi; B. Elleuch

2009-01-01

97

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, ...

98

Electrochemical deposition of green rust on zero-valent iron  

E-print Network

surface oxy- hydroxides of iron were removed. This was assumed to have occurred, when the washing solution contained less than 10 mg/l Fe(II). The washed ZVI was transferred into a test tube containing Endox solution to dissolve the oxy-hydroxides bound... with adequate accuracy and precision in the presence of Endox. These experiments were conducted by measuring Fe(II) in multiple samples at neutral pH in deaerated deionized water with different concentrations (0.5 mg/l, 2.5 mg/l, 5.0 mg/l, 7.5 mg/l and 10...

Kulkarni, Dhananjay Vijay

2006-08-16

99

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

PubMed

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

Wilkin, Richard T; McNeil, Mary S

2003-11-01

100

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

NASA Astrophysics Data System (ADS)

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).

Filip, Jan; Kašlík, Josef; Med?ík, Ivo; Petala, Eleni; Zbo?il, Radek; Slunský, Jan; ?erník, Miroslav; Stav?lová, Monika

2014-05-01

101

Zero-Valent Metal Emulsion for Reductive Dehalogenation of DNAPLs  

NASA Technical Reports Server (NTRS)

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.

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

2006-01-01

102

Zero-Valent Metal Emulsion for Reductive Dehalogenation of DNAPLS  

NASA Technical Reports Server (NTRS)

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

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

2003-01-01

103

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

NASA Astrophysics Data System (ADS)

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.

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

2014-04-01

104

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

SciTech Connect

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, ev

Fogwell, Thomas W. [Fogwell Consulting, P.O. Box 20221, Piedmont, CA 94620 (United States)] [Fogwell Consulting, P.O. Box 20221, Piedmont, CA 94620 (United States); Santina, Pete [SMI-PS, Inc., 2073 Prado Vista, Lincoln, CA 95648 (United States)] [SMI-PS, Inc., 2073 Prado Vista, Lincoln, CA 95648 (United States)

2013-07-01

105

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

SciTech Connect

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.

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

106

Field Demonstration of DNAPL Dehalogenation Using Emulsified Zero-Valent Iron  

NASA Technical Reports Server (NTRS)

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.

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

107

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

PubMed

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. PMID:15787371

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

2005-03-01

108

Field demonstration of DNAPL dehalogenation using emulsified zero-valent iron  

NASA Technical Reports Server (NTRS)

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.

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

109

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

PubMed

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. PMID:17113680

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

2007-02-20

110

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

NASA Astrophysics Data System (ADS)

The successful dechlorination of mixtures of chlorinated hydrocarbons with zero-valent metals requires information concerning the kinetics of simultaneous degradation of different contaminants. This includes intraspecies competitive effects (loading of the reactive iron surface by a single contaminant) as well as interspecies competition of several contaminants for the reactive sites available. In columns packed with zero-valent iron, the degradation behaviour of trichloroethylene (TCE), cis-dichloroethylene (DCE) and mixtures of both was measured in order to investigate interspecies competition. Although a decreasing rate of dechlorination is to be expected, when several degradable substances compete for the reactive sites on the iron surface, TCE degradation is nearly unaffected by the presence of cis-DCE. In contrast, cis-DCE degradation rates decrease significantly when TCE is added. A new modelling approach is developed in order to identify and quantify the observed competitive effects. The numerical model TBC (Transport, Biochemistry and Chemistry, Schäfer et al., 1998a) is used to describe adsorption, desorption and dechlorination in a mechanistic way. Adsorption and degradation of a contaminant based on a limited number of reactive sites leads to a combined zero- and first-order degradation kinetics for high and low concentrations, respectively. The adsorption of several contaminants with different sorption parameters to a limited reactive surface causes interspecies competition. The reaction scheme and the parameters required are successfully transferred from Arnold and Roberts (2000b) to the model TBC. The degradation behaviour of the mixed contamination observed in the column experiments can be related to the adsorption properties of TCE and cis-DCE. By predicting the degradation of the single substances TCE and cis-DCE as well as mixtures of both, the calibrated model is used to investigate the effects of interspecies competition on the design of permeable reactive iron barriers. Even if TCE is present in only small concentrations (>3% of molar cis-DCE concentration) it is the contaminant limiting the residence time and the required thickness of the iron barrier.

Schäfer, Dirk; Köber, Ralf; Dahmke, Andreas

2003-09-01

111

Isotopic fractionation during reductive dechlorination of trichloroethene by zero-valent iron: influence of surface treatment.  

PubMed

During reductive dechlorination of trichloroethene (TCE) by zero-valent iron, stable carbon isotopic values of residual TCE fractionate significantly and can be described by a Rayleigh model. This study investigated the effect of observed reaction rate, surface oxidation and iron type on isotopic fractionation of TCE during reductive dechlorination. Variation of observed reaction rate did not produce significant differences in isotopic fractionation in degradation experiments. However, a small influence on isotopic fractionation was observed for experiments using acid-cleaned electrolytic iron versus experiments using autoclaved electrolytic iron, acid-cleaned Peerless cast iron or autoclaved Peerless cast iron. A consistent isotopic enrichment factor of epsilon = -16.7/1000 was determined for all experiments using cast iron, and for the experiments with autoclaved electrolytic iron. Column experiments using 100% cast iron and a 28% cast iron/72% aquifer matrix mixture also resulted in an enrichment factor of -16.9/1000. The consistency in enrichment factors between batch and column systems suggests that isotopic trends observed in batch systems may be extrapolated to flowing systems such as field sites. The fact that significant isotopic fractionation was observed in all experiments implies that isotopic analysis can provide a direct qualitative indication of whether or not reductive dechlorination of TCE by Fe0 is occurring. This evidence may be useful in answering questions which arise at field sites, such as determining whether TCE observed down-gradient of an iron wall remediation scheme is the result of incomplete degradation within the wall, or of the dissolved TCE plume by passing the wall. PMID:12430646

Slater, G F; Lollar, B Sherwood; King, R Allen; O'Hannesin, S

2002-11-01

112

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

NASA Astrophysics Data System (ADS)

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.

Sun, Fenglong

113

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

Microsoft Academic Search

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 CaSOâ, 5 mM CaClâ, or 5 mM Ca(NOâ)â. At early elapsed times, TCE reaction rates were pseudo-first-order in TCE concentration

James Farrell; Mark Kason; Nicos Melitas; Tie Li

2000-01-01

114

Bactericidal Effect of Zero-Valent Iron Nanoparticles on Escherichia coli  

PubMed Central

Zero-valent iron nanoparticles (nano-Fe0) in aqueous solution rapidly inactivated Escherichia coli (E. coli). A strong bactericidal effect of nano-Fe0 was found under deaerated conditions, with a linear correlation between log inactivation and nano-Fe0 dose (0.82 log inactivation / mg/L nano-Fe0 · hr). The inactivation of E. coli under air saturation required much higher nano-Fe0 doses due to the corrosion and surface oxidation of nano-Fe0 by dissolved oxygen. Significant physical disruption of the cell membranes was observed in E. coli exposed to nano-Fe0, which may have caused the inactivation, or enhanced the biocidal effects of dissolved iron. The reaction of Fe(II) with intracellular oxygen or hydrogen peroxide also may have induced oxidative stress by producing reactive oxygen species. The bactericidal effect of nano-Fe0 was a unique property of nano-Fe0, which was not observed in other types of iron-based compounds. PMID:18678028

Lee, Changha; Kim, Jee Yeon; Lee, Won Il; Nelson, Kara L.; Yoon, Jeyong; Sedlak, David L.

2008-01-01

115

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

PubMed

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

Daoud, Waseem; Ebadi, Taghi; Fahimifar, Ahmad

2015-03-01

116

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

PubMed

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 24ppm 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)=643ppm, and the saturation sorption of 8173mgU/g ZVI-nps was achieved at C0(U)=714ppm. 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

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

117

Zero valent iron simultaneously enhances methane production and sulfate reduction in anaerobic granular sludge reactors.  

PubMed

Zero valent iron (ZVI) packed anaerobic granular sludge reactors have been developed for improved anaerobic wastewater treatment. In this work, a mathematical model is developed to describe the enhanced methane production and sulfate reduction in anaerobic granular sludge reactors with the addition of ZVI. The model is successfully calibrated and validated using long-term experimental data sets from two independent ZVI-enhanced anaerobic granular sludge reactors with different operational conditions. The model satisfactorily describes the chemical oxygen demand (COD) removal, sulfate reduction and methane production data from both systems. Results show ZVI directly promotes propionate degradation and methanogenesis to enhance methane production. Simultaneously, ZVI alleviates the inhibition of un-dissociated H2S on acetogens, methanogens and sulfate reducing bacteria (SRB) through buffering pH (Fe(0) + 2H(+) = Fe(2+) + H2) and iron sulfide precipitation, which improve the sulfate reduction capacity, especially under deterioration conditions. In addition, the enhancement of ZVI on methane production and sulfate reduction occurs mainly at relatively low COD/ [Formula: see text] ratio (e.g., 2-4.5) rather than high COD/ [Formula: see text] ratio (e.g., 16.7) compared to the reactor without ZVI addition. The model proposed in this work is expected to provide support for further development of a more efficient ZVI-based anaerobic granular system. PMID:25867207

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

2015-05-15

118

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

NASA Astrophysics Data System (ADS)

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.

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

2009-09-01

119

Enhanced paramagnetic Cu²? ions removal by coupling a weak magnetic field with zero valent iron.  

PubMed

A weak magnetic field (WMF) was proposed to enhance paramagnetic Cu(2+) ions removal by zero valent iron (ZVI). The rate constants of Cu(2+) removal by ZVI with WMF at pH 3.0-6.0 were -10.8 to -383.7 fold greater than those without WMF. XRD and XPS analyses revealed that applying a WMF enhanced both the Cu(2+) adsorption to the ZVI surface and the transformation of Cu(2+) to Cu(0) by ZVI. The enhanced Cu(2+) sequestration by ZVI with WMF was accompanied with expedited ZVI corrosion and solution ORP drop. The uneven distribution of paramagnetic Cu(2+) along an iron wire in an inhomogeneous MF verified that the magnetic field gradient force would accelerate the paramagnetic Cu(2+) transportation toward the ZVI surface due to the WMF-induced sharp decay of magnetic flux intensity from ZVI surface to bulk Cu(2+) solution. The paramagnetic Fe(2+) ions generated by ZVI corrosion would also accumulate at the position with the highest magnetic flux intensity on the ZVI surface, causing uneven distribution of Fe(2+), and facilitate the local galvanic corrosion of ZVI, and thus, Cu(2+) reduction by ZVI. The electrochemical analysis verified that the accelerated ZVI corrosion in the presence of WMF partly arose from the Lorentz force-enhanced mass transfer. PMID:25464332

Jiang, Xiao; Qiao, Junlian; Lo, Irene M C; Wang, Lei; Guan, Xiaohong; Lu, Zhanpeng; Zhou, Gongming; Xu, Chunhua

2015-02-11

120

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

PubMed

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

An, Yi; Dong, Qi; Zhang, Keqiang

2014-05-01

121

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 ...

122

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...

123

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

Microsoft Academic Search

Fluidized zero valent iron (ZVI) process was conducted to reduce hexavalent chromium (chromate, CrO42?) to trivalent chromium (Cr3+) from electroplating wastewater due to the following reasons: (1) Extremely low pH (1–2) for the electroplating wastewater favoring the ZVI reaction. (2) The ferric ion, produced from the reaction of Cr(VI) and ZVI, can act as a coagulant to assist the precipitation

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

2007-01-01

124

Effect of zero-valent iron and a redox mediator on removal of selenium in agricultural drainage water  

Microsoft Academic Search

Effective and economical removal of selenium (Se) in agricultural drainage water is very important in Se bioremediation. Zero-valent iron (ZVI) and a redox mediator [anthraquinone-2,6-disulfonate (AQDS)] were assessed for their ability to enhance the removal of Se(VI) or Se(IV) (500 µg\\/L) in synthetic drainage water by Enterobacter taylorae. The results showed that E. taylorae was capable of using inexpensive sucrose to

Yiqiang Zhang; Christopher Amrhein; Andrew Chang; William T. Frankenberger

2008-01-01

125

Enhanced chromium (VI) removal using activated carbon modified by zero valent iron and silver bimetallic nanoparticles.  

PubMed

Recently, adsorption process has been introduced as a favorable and effective technique for the removal of metal ions from aqueous solutions. In the present study, bimetallic nanoparticles consisting of zero valent iron and silver were loaded on the activated carbon powder for the preparation of a new adsorbent (PAC-Fe(o)/Ag). The above adsorbent was characterized by using XRD, SEM and TEM techniqes. Experimental data were exploited for kinetic, equilibrium and thermodynamic evaluations related to the adsorption processes. The Cr(VI) adsorption process was found to be favorable at pH 3 and it reached equilibrium state within 60 min. The stirring rate did not have a significant effect on the adsorption efficiency. Furthermore, the monolayer adsorption capacity of Cr(VI) based on the Langmuir model was measured to be 100 mg/g. The experimental equilibrium data were fitted to the Freundlich adsorption and pseudo second-order models. According to the thermodynamic study, the adsorption process was spontaneous and endothermic in nature, indicating the adsorption capacity increases with increasing the temperature. The results also revealed that the synthesized composite can be potentially applied as a magnetic adsorbent to remove Cr(VI) contaminants from aqueous solutions. PMID:25184050

Kakavandi, Babak; Kalantary, Roshanak Rezaei; Farzadkia, Mahdi; Mahvi, Amir Hossein; Esrafili, Ali; Azari, Ali; Yari, Ahmad Reza; Javid, Allah Bakhsh

2014-01-01

126

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

PubMed

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

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

2010-04-15

127

Enhanced degradation of carbon tetrachloride by surfactant-modified zero-valent iron*  

PubMed Central

Sorption of carbon tetrachloride (CT) by zero-valent iron (ZVI) is the rate-limiting step in the degradation of CT, so the sorption capacity of ZVI is of great importance. This experiment was aimed at enhancing the sorption of CT by ZVI and the degradation rate of CT by modification of surfactants. This study showed that ZVI modified by cationic surfactants has favorable synergistic effect on the degradation of CT. The CT degradation rate of ZVI modified by cetyl pyridinium bromide (CPB) was higher than that of the unmodified ZVI by 130%, and the CT degradation rate of ZVI modified by cetyl trimethyl ammonium bromide (CTAB) was higher than that of the unmodified ZVI by 81%. This study also showed that the best degradation effect is obtained at the near critical micelle concentrations (CMC) and that high loaded cationic surfactant does not have good synergistic effect on the degradation due to its hydrophilicity and the block in surface reduction sites. Furthermore degradation of CT by ZVI modified by nonionic surfactant has not positive effect on the degradation as the ionic surfactant and the ZVI modified by anionic surfactant has hardly any obvious effects on the degradation. PMID:16909470

Meng, Ya-feng; Guan, Bao-hong; Wu, Zhong-biao; Wang, Da-hui

2006-01-01

128

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

SciTech Connect

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.

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

129

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

PubMed

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

Bayer, Peter; Finkel, Michael

2005-06-01

130

Competition for sorption and degradation of chlorinated ethenes in batch zero-valent iron systems.  

PubMed

The sorption and degradation of the chlorinated ethenes tetrachloroethene (PCE, 5 mg L(-1)) and trichloroethene (TCE, 10 mg L(-1)) were investigated in zero-valent iron systems (ZVI, 100 g L(-1)) in the presence of compounds common to contaminated groundwater with varying physicochemical properties. The potential competitors were chlorinated ethenes, monocyclic aromatic hydrocarbons, and humic acids. The effect of a complex matrix was tested with landfill contaminated groundwater. Nonlinear Freundlich isotherms adequately described chloroethene sorption to ZVI. In the presence of the more hydrophobic PCE (5 mg L(-1)), TCE sorption and degradation decreased by 33% and 30%, respectively, while TCE (10 mg L(-1)) decreased PCE degradation by 30%. In the presence of nonreactive hydrophobic hydrocarbons (i.e., benzene, toluene, and m-xylene at 100 mg L(-1)), TCE and PCE sorption decreased by 73% and 55%, respectively. The presence of the hydrocarbons had no effect on TCE degradation and increased PCE reduction rates by 50%, suggesting that the displacement of the chloroethenes from the sorption sites by the aromatic hydrocarbons enhanced the degradation rates. Humic acids did not interfere significantly with chloroethene sorption or with TCE degradation but lowered PCE degradation kinetics by 36% when present at high concentrations (100 mg L(-1)). The landfill groundwater with an organic carbon content of 109 mg L(-1) C had no effect on chloroethene sorption but inhibited TCE and PCE degradation by 60% and 70%, respectively. PMID:15212263

Dries, Jan; Bastiaens, Leen; Springael, Dirk; Agathos, Spiros N; Diels, Ludo

2004-05-15

131

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

PubMed Central

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

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

2014-01-01

132

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

PubMed

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

Ma, Xingmao; Gurung, Arun; Deng, Yang

2013-01-15

133

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

SciTech Connect

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.

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

2010-01-01

134

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

PubMed

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

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

2014-12-01

135

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

PubMed

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

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

2012-05-15

136

Conceptual comparison of pink water treatment technologies: granular activated carbon, anaerobic fluidized bed, and zero-valent iron-Fenton process  

Microsoft Academic Search

Pink water, explosive-laden wastewater produced in army ammunition plants is often treated using expensive and non-destructive granular activated carbon (GAC) adsorption. This paper compares GAC adsorption and two alternative treatment technologies, anaerobic GAC fluidized bed reactor and zero- valent iron-Fenton process. The bench-scale demonstration of the zero-valent iron-Fenton process with real pink water is reported. The features of three technologies

S.-Y. Oh; D. K. Cha; P. C. Chiu; B. J. Kim

137

A novel conditioning process for enhancing dewaterability of waste activated sludge by combination of zero-valent iron and persulfate.  

PubMed

Improvement of sludge dewaterability is crucial for reducing the costs of sludge disposal in wastewater treatment plants. This study presents a novel conditioning method for improving waste activated sludge dewaterability by combination of persulfate and zero-valent iron. The combination of zero-valent iron (0-30g/L) and persulfate (0-6g/L) under neutral pH substantially enhanced the sludge dewaterability due to the advanced oxidization reactions. The highest enhancement of sludge dewaterability was achieved at 4g persulfate/L and 15g zero-valent iron/L, with which the capillary suction time was reduced by over 50%. The release of soluble chemical oxygen demand during the conditioning process implied the decomposition of sludge structure and microorganisms, which facilitated the improvement of dewaterability due to the release of bound water that was included in sludge structure and microorganism. Economic analysis showed that the proposed conditioning process with persulfate and ZVI is more economically favorable for improving WAS dewaterability than classical Fenton reagent. PMID:25804531

Zhou, Xu; Wang, Qilin; Jiang, Guangming; Liu, Peng; Yuan, Zhiguo

2015-06-01

138

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

PubMed

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 ((12)C) and heavier ((13)C) isotopes. The simulation of a column experiment involving the parallel degradation of TCE by hydrogenolysis and beta-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. PMID:18267347

Prommer, Henning; Aziz, Lidia H; Bolaño, Nerea; Taubald, Heinrich; Schüth, Christoph

2008-04-01

139

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

NASA Astrophysics Data System (ADS)

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.

Prommer, Henning; Aziz, Lidia H.; Bolaño, Nerea; Taubald, Heinrich; Schüth, Christoph

2008-04-01

140

Effects of pH and particle size on kinetics of nitrobenzene reduction by zero-valent iron.  

PubMed

Nitrobenzene has been considered as a significant groundwater contaminant due to its wide usage in explosives, insecticides, herbicides, pharmaceuticals and dyes. Nitrobenzene is of environmental concern because of its toxicity. In the presence of zero-valent iron (ZVI), reduction of the nitro group is the dominant transformation process for nitrobenzene. A series of experiments were carried out to investigate the kinetics of nitrobenzene reduction by ZVI and the effects of pH and ZVI particle size on nitrobenzene removal in groundwater. The results indicated that nitrobenzene could be reduced to aniline by ZVI; the reduction of nitrobenzene by ZVI followed a pseudo first-order kinetics; the observed nitrobenzene reduction rate constant (k(obs)) was 0.0006 min(-1) and the half-life of nitrobenzene (t1/2) was 115.5 min; the mass balance achieved 87.5% for nitrobenzene reduction by the 1 mm ZVI particle and the final removal efficiency was 80.98%. In addition, the pH and ZVI particle size were found to exhibit significant influences on the nitrobenzene reduction. The observed nitrobenzene reduction rate constant linearly decreased with increase pH and the data fitted on polynomial regression equation for the observed nitrobenzene reduction rate constant and ZVI particle size. Therefore, use of ZVI based permeable reactive barrier technology to remedy nitrobenzene contaminated groundwater was feasible. PMID:21235162

Dong, Jun; Zhao, Yongsheng; Zhao, Ran; Zhou, Rui

2010-01-01

141

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

PubMed Central

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 Å. 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 Å. 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

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

2010-01-01

142

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

PubMed

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

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

2014-08-01

143

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

NASA Astrophysics Data System (ADS)

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.

Busch, Jan; Oswald, Sascha

2013-04-01

144

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

PubMed

The use of nanoscale zero-valent iron (nZVI) as a new tool for the treatment of polluted soils and groundwater has received considerable attention in recent years due to its high reactivity, in situ application and cost-effectiveness. The objectives of this study were to investigate the effectiveness of using a commercial stabilised suspension of nZVI to immobilise As in brownfield soil and to investigate its impact on Fe availability in the treated soil. The phytotoxicities of the soil samples were also evaluated using a germination test with two plant species: barley (Hordeum vulgare L) and common vetch (Vicia sativa L). Two doses of the commercial nZVI suspension were studied, 1% and 10%, and two soil-nanoparticle interaction times, 72 h and 3 mo, were used to compare the stabilities of the soils treated with nZVI. The As availability was evaluated using a sequential extraction procedure and the toxicity characteristics leaching procedure (TCLP) test. The application of nZVI significantly decreased the availability of As in the soil. The immobilisation of As was more effective and more stable over time with the 10% dose than with the 1% dose of the commercial nZVI suspension. The application of nZVI did not induce an important increase in Fe mobility because the Fe leachability was less than 2 mg L(-1) over the time period studied. The lower availability of As in the soil led to a decrease in the phytotoxicity of the soil to barley and vetch germination. Thus, the proposed nanotechnology could be a potential alternative for the in situ remediation of As-polluted soils and could be combined with remediation processes where plants are involved. PMID:25072767

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

2014-01-01

145

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

SciTech Connect

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.

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

2013-09-01

146

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

NASA Astrophysics Data System (ADS)

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

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

2007-12-01

147

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

SciTech Connect

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.

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

2005-12-22

148

Effectiveness of nanoscale zero-valent iron for treatment of a PCE-DNAPL source zone  

NASA Astrophysics Data System (ADS)

Nanoscale zero-valent iron (nZVI) has received considerable attention as a potential in situ remediation technology for treating chlorinated solvent source zones. Experimental and mathematical modeling studies were conducted to investigate the performance of nZVI in the transformation of tetrachloroethene (PCE) entrapped as a dense nonaqueous phase liquid (DNAPL). Injection of a 60 g/L suspension of nZVI into a column containing 20-30 mesh Ottawa sand and PCE-DNAPL at a residual saturation of 5.5% resulted in a uniform distribution of nZVI and minimal displacement of PCE. Subsequent flushing with 267 pore volumes of water containing 3 mM CaCl 2 at a Darcy velocity of 0.75 m/day resulted in steady-state effluent concentrations of PCE near the solubility limit (ca. 200 mg/L) and production of dissolved-phase ethene (10-30 mg/L). Over the duration of the experiment, approximately 30% of the initial PCE-DNAPL mass reacted to form ethene, 50% was eluted as dissolved-phase PCE, and 20% remained in the column as PCE-DNAPL. To further explore the implications of the nZVI column results, a multiphase transport model was developed that incorporated rate-limited PCE-DNAPL dissolution and reactions with nZVI. Using a fitted pseudo first-order transformation rate coefficient of 1.42 1/h, the model accurately captured observed trends in effluent concentrations of PCE and ethene and overall mass balance. A model sensitivity study reveals a strong dependence of treatment effectiveness on system characteristics. The sensitivity analysis suggests that an increase in the extent of PCE transformation is facilitated by decreasing flow rate, emplacement of nZVI down-gradient of the DNAPL source zone, and decreasing length of the DNAPL source zone. These findings indicate that, although emplacement of high concentrations of nZVI within a PCE-DNAPL source zone can result in substantial transformation of the parent compound, careful attention to design parameters (e.g. flow rate, location and amount nZVI delivered) will be required to achieve complete conversion to benign reaction products.

Taghavy, Amir; Costanza, Jed; Pennell, Kurt D.; Abriola, Linda M.

2010-11-01

149

[Treatment of Cr( VI) in deoxygenated simulated groundwater using nanoscale zero-valent iron].  

PubMed

Laboratory experiments and theoretical modeling studies were performed to investigate the mechanisms of Cr( VI) removal from deoxygenated simulated groundwater using nanoscale zero-valent iron, and to evaluate influencing factors and kinetics based on zeta potential, redox potential, ferrous concentrations, and the pe-pH diagram of Fe-Cr-H2O system. Experimental results demonstrate that the removal efficiency of Cr(VI) decreases with the increasing Cr( VI)/Fe mass ratio. When the Cr(VI)/Fe mass ratios are 0.025, 0.050, 0.075, and 0.100, the corresponding Cr(VI) removal rates are 100.0%, 85.6%, 72.7% and 39.6%, respectively. The Cr( VI) removal is favorable at acidic pH with fixed Cr(VI)/Fe mass ratio of 0.100. When pH are 3.0, 5.0, 7.0, 9.0 and 11.0, the Cr(VI) removal rates are 73.4%, 57.6%, 39.6%, 44.1%, and 41.2%, accordingly. The Cr(VI) removal follows the pseudo second-order kinetics. When pH is 7.0 and Cr(VI)/nZVI mass ratio is 0.025, the rate of Cr(VI) removal is the highest with rate constant at 9.76 x 10(-3) g x (mg x min)(-1). The conversion from Cr2O7(2-) to Cr3+ should be instantaneous when Cr2O7(2-) is absorbed on the surface of Fe. The Cr(VI) was reduced to Cr(III), which was subsequently incorporated into the FeOOH shell and formed a Cr-Fe film. The film once formed could further inhibit the electron transfer between Cr2O7(2-) and Fe. Then Cr(V) removal was primary controlled by the adsorption process. PMID:20358821

Wu, Jia; Tian, Xiu-jun; Wang, Jin; Jing, Chuan-yong

2010-03-01

150

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

NASA Astrophysics Data System (ADS)

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.

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

2014-05-01

151

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

PubMed

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

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

2015-03-15

152

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

NASA Astrophysics Data System (ADS)

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.

Zabetakis, Kara M.

153

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

NASA Astrophysics Data System (ADS)

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.

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

2012-04-01

154

Advantages of low pH and limited oxygenation in arsenite removal from water by zero-valent iron.  

PubMed

The removal of toxic arsenic species from contaminated waters by zero-valent iron (ZVI) has drawn considerable attention in recent years. In this approach, arsenic ions are mainly removed by adsorption to the iron corrosion products. Reduction to zero-valent arsenic on the ZVI surface is possible in the absence of competing oxidants and can reduce arsenic mobility and sludge formation. However, associated removal rates are relatively low. In the current study, simultaneous high reduction and removal rates of arsenite (H3AsO3), the more toxic and mobile environmentally occurring arsenic species, was demonstrated by reacting it with ZVI under limited aeration and relatively low pH. 90% of the removed arsenic was attached to the ZVI particles and 60% of which was in the elemental state. Under the same non-acidic conditions, only 40-60% of the removed arsenic was attached to the ZVI with no change in arsenic oxidation state. Under anaerobic conditions, reduction occurred but total arsenic removal rate was significantly lower and ZVI demand was higher. The effective arsenite removal under acidic oxygen-limited conditions was explained by formation of Fe(II)-solid intermediate on the ZVI surface that provided high surface area and reducing power. PMID:23500792

Klas, Sivan; Kirk, Donald W

2013-05-15

155

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

NASA Astrophysics Data System (ADS)

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.

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

2014-04-01

156

Removal of heavy metals and dyes by supported nano zero-valent iron on barium ferrite microfibers.  

PubMed

The binary nano zero-valent iron/barium ferrite (NZVI/BFO) microfibers with uniform diameters and high porosity were prepared by the organic gel-thermal selective reduction process. The composite microfibers are fabricated from nano zero-valent iron and nano BaFe12O19 grains. The effects of pH, adsorbent dosage, and contact time on the adsorption of heavy metals and dyes have been investigated. The adsorption isotherms of heavy metals and dyes on the microfibers are well described by the Langmuir model, in which the estimated adsorption capacities are 14.5, 29.9, 68.3 and 110.4 mg/g for Pb(II), As(V), Congo red and methylene blue, respectively. After five cycles, these microfibers still exhibit a high removal efficiency for As(V), Pb(II), Congo red and methylene blue. The enhanced adsorption characteristics can be attributed to the porous structure, strong surface activity and electronic hopping. Therefore, the magnetic NZVI/BFO microfibers can be used as an efficient, fast and high capacity adsorbent for heavy metals and dyes removal. PMID:24758012

Yang, Xinchun; Shen, Xiangqian; Jing, Maoxiang; Liu, Ruijiang; Lu, Yi; Xiang, Jun

2014-07-01

157

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...

158

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

SciTech Connect

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.

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

2006-03-20

159

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

NASA Astrophysics Data System (ADS)

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.

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

2014-12-01

160

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

PubMed

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

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

2011-01-01

161

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

PubMed

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

Reardon, Eric J

2014-02-01

162

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

NASA Astrophysics Data System (ADS)

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.

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

2007-12-01

163

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

PubMed

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

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

2015-01-01

164

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)

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.

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

2015-02-01

165

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

PubMed Central

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

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

2015-01-01

166

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

PubMed

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

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

2014-08-01

167

Influence of nanoscale zero-valent iron on geochemical properties of groundwater and vinyl chloride degradation: A field case study.  

PubMed

A 200m(2) pilot-scale field test successfully demonstrated the use of nanoscale zero-valent iron (NZVI) for effective remediation of groundwater contaminated with chlorinated organic compounds in Taiwan within six months. Both commercially available and on-site synthesized NZVI were used. A well-defined monitoring program allowing to collect three-dimensional spatial data from 13 nested multi-level monitoring wells was conducted to monitor geochemical parameters in groundwater. The degradation efficiency of vinyl chloride (VC) determined at most of monitoring wells was 50-99%. It was found that the injection of NZVI caused a significant change in total iron, total solid (TS) and suspended solid (SS) concentrations in groundwater. Total iron concentration showed a moderate and weak correlation with SS and TS, respectively, suggesting that SS may be used to indicate the NZVI distribution in groundwater. A decrease in oxidation-reduction potential (ORP) values from about -100 to -400mV after NZVI injection was observed. This revealed that NZVI is an effective means of achieving highly reducing conditions in the subsurface environment. Both VC degradation efficiency and ORP showed a correlative tendency as an increase in VC degradation efficiency corresponded to a decrease of ORP. This is in agreement with the previous studies suggesting that ORP can serve as an indicator for the NZVI reactivity. PMID:19800096

Wei, Yu-Ting; Wu, Shian-Chee; Chou, Chih-Ming; Che, Choi-Hong; Tsai, Shin-Mu; Lien, Hsing-Lung

2010-01-01

168

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

PubMed

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

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

2015-01-01

169

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

PubMed

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

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

2011-01-01

170

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

PubMed

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

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

2014-12-01

171

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

PubMed

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, Fe²? reacted preferably with hydroxide ions to form ferrous hydroxide which is the precursor of magnetite. As a result only minor passivation of the reactive nZVI was observed. PMID:25462777

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

2015-01-01

172

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

PubMed

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

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

2007-04-01

173

Dechlorination of PCBs in the simulative transformer oil by microwave-hydrothermal reaction with zero-valent iron involved.  

PubMed

The conventional hydrothermal reaction with iron powder, NaOH and H(2)O as reactants was reported to occur at temperature above 423K, and iron oxides (Fe(3)O(4) and NaFeO(2)) and hydrogen were produced. In this study, microwave heating was adopted to take the place of conventional heating to induce the hydrothermal reaction. Under microwave irradiation, NaOH and H(2)O absorbed microwave energy by space charge polarization and dipolar polarization and instantly converted it into thermal energy, which initiated the hydrothermal reaction that involved with zero-valent iron. X-ray diffraction (XRD) analysis found Fe(3)O(4)/NaFeO(2) and confirmed the occurrence of microwave-induced hydrothermal reaction. The developed microwave-hydrothermal reaction was employed for the dechlorination of PCBs. Hexadecane containing 100mgL(-1) of Aroclor1254 was used as simulative transformer oil, and the dechlorination of PCBs was evaluated by GC/ECD, GC/MS and ion chromatography. For PCBs in 10mL simulative transformer oil, almost complete dechlorination was achieved by 750W microwave irradiation for 10min, with 0.3g iron powder, 0.3g NaOH and 0.6mL H(2)O added. The effects of important factors including microwave power and the amounts of reactants added, on the dechlorination degree were investigated, moreover, the dechlorination mechanism was suggested. Microwave irradiation combined with the common and cheap materials, iron powder, NaOH and H(2)O, might provide a fast and cost-effective method for the treatment of PCBs-containing wastes. PMID:21074824

Liu, Xitao; Zhao, Wei; Sun, Ke; Zhang, Guixiang; Zhao, Ye

2011-01-01

174

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

PubMed

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 (40-70nm 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

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

2015-04-01

175

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

PubMed

Improvement of sludge dewaterability is crucial for reducing the costs of sludge disposal in wastewater treatment plants. This study presents a novel method based on combined conditioning with zero-valent iron (ZVI) and hydrogen peroxide (HP) at pH 2.0 to improve dewaterability of a full-scale waste activated sludge (WAS). The combination of ZVI (0-750mg/L) and HP (0-750mg/L) at pH 2.0 substantially improved the WAS dewaterability due to Fenton-like reactions. The highest improvement in WAS dewaterability was attained at 500mg ZVI/L and 250mg HP/L, when the capillary suction time of the WAS was reduced by approximately 50%. Particle size distribution indicated that the sludge flocs were decomposed after conditioning. Economic analysis showed that combined conditioning with ZVI and HP was a more economically favorable method for improving WAS dewaterability than the classical Fenton reaction based method initiated by ferrous salts and HP. PMID:25463788

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

2014-12-01

176

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

PubMed

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

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

2014-12-01

177

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

PubMed

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

Kowalski, Krzysztof P; Søgaard, Erik G

2014-12-01

178

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

PubMed

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

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

2015-02-01

179

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

PubMed

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

Wu, Yan; Luo, Hanjin; Wang, Hou

2014-01-01

180

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

PubMed

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

Xu, Guiying; Wang, Jiangbo; Lu, Mang

2014-12-01

181

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

PubMed

Magnetite nanoparticles were used as an additive material in a zero-valent iron (Fe(0)) reaction to reduce nitrate in groundwater and its effects on nitrate removal were investigated. The addition of nano-sized magnetite (NMT) to Fe(0) 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 Fe(0) surface due to their magnetic properties. The rate enhancement effect of NMT is presumed to arise from its role as a corrosion promoter for Fe(0) corrosion as well as an electron mediator that facilitated electron transport from Fe(0) to adsorbed nitrate. Nitrate reduction by Fe(0) 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., Ca(2+) and Mg(2+), in the Fe(0)-H2O interface that promoted electrostatic attraction of nitrate to the reaction sites. Moreover, the addition of NMT imparted superior longevity to Fe(0), 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 Fe(0)/NMT system in the treatment of nitrate-contaminated GW. PMID:25665757

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

2015-04-01

182

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

PubMed Central

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

2014-01-01

183

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

PubMed

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

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

2014-08-15

184

The role of clay minerals in the reduction of nitrate in groundwater by zero-valent iron.  

PubMed

Bench-scale batch experiments were performed to investigate the feasibility of using different types of clay minerals (bentonite, fuller's earth, and biotite) with zero-valent iron for their potential utility in enhancing nitrate reduction and ammonium control. Kinetics experiments performed with deionized water (DW) and groundwater (GW) revealed nitrate reduction by Fe(0) proceeded at significantly faster rate in GW than in DW, and such a difference was attributed to the formation of green rust in GW. The amendment of the minerals at the dose of 25 g L(-1) in Fe(0) reaction in GW resulted in approximately 41%, 43%, and 33% more removal of nitrate in 64 h reaction for bentonite, fuller's earth, and biotite, respectively, compared to Fe(0) alone reaction. The presumed role of the minerals in the rate enhancement was to provide sites for the formation of surface bound green rust. Bentonite and fuller's earth also effectively removed ammonium produced from nitrate reduction by adsorption, with the removal efficiencies significantly increased with the increase in mineral dose above 5:1 Fe(0) to mineral mass ratio. Such a removal of ammonium was not observed for biotite, presumably due to its lack of swelling property. Equilibrium adsorption experiments indicated bentonite and fuller's earth had maximum ammonium adsorption capacity of 5.6 and 2.1 mg g(-1), respectively. PMID:20797759

Cho, Dong-Wan; Chon, Chul-Min; Jeon, Byong-Hun; Kim, Yongje; Khan, Moonis Ali; Song, Hocheol

2010-10-01

185

Coupled effects of aging and weak magnetic fields on sequestration of selenite by zero-valent iron.  

PubMed

The sequestration of Se(IV) by zero-valent iron (ZVI) is strongly influenced by the coupled effects of aging ZVI and the presence of a weak magnetic field (WMF). ZVI aged at pH 6.0 with MES as buffer between 6 and 60 h gave nearly constant rates of Se(IV) removal with WMF but with rate constants that are 10- to 100-fold greater than without. XANES analysis showed that applying WMF changes the mechanism of Se(IV) removal by ZVI aged for 6-60 h from adsorption followed by reduction to direct reduction. The strong correlation between Se(IV) removal and Fe2+ release suggests direct reduction of Se(IV) to Se(0) by Fe0, in agreement with the XANES analysis. The numerical simulation of ZVI magnetization revealed that the WMF influence on Se(IV) sequestration is associated mainly with the ferromagnetism of ZVI and the paramagnetism of Fe2+. In the presence of the WMF, the Lorentz force gives rise to convection in the solution, which narrows the diffusion layer, and the field gradient force, which tends to move paramagnetic ions (esp. Fe2+) along the higher field gradient at the ZVI particle surface, thereby inducing nonuniform depassivation and eventually localized corrosion of the ZVI surface. PMID:24804570

Liang, Liping; Guan, Xiaohong; Shi, Zhong; Li, Jialing; Wu, Yinan; Tratnyek, Paul G

2014-06-01

186

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

PubMed

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

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

2010-11-01

187

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

PubMed

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

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

2015-03-01

188

Trichloroethene (TCE) Degradation using Granular Activated Carbon and Zero Valent Iron Particles  

E-print Network

methods of TCE removal include Permeable Reactive Barriers (PRB), Bioremediation and Solvent Extraction, and Dionysios D. Dionysiou, Synthesis of Reactive Nano- Fe/Pd Bimetallic System-Impregnated Activated Carbon

Barthelat, Francois

189

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

PubMed

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 Ag–S 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

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

190

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

PubMed

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

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

2014-08-01

191

Nanoscale zero-valent iron application for in situ reduction of hexavalent chromium and its effects on indigenous microorganism populations.  

PubMed

Because of its high toxicity and mobility, hexavalent chromium is considered to be a high priority pollutant. This study was performed to carry out a pilot-scale in-situ remediation test in the saturated zone of a historically Cr(VI)-contaminated site using commercially available nanoscale zero-valent iron (nZVI). The site was monitored before and after the nZVI application by means of microbial cultivation tests, phospholipid fatty acid analysis (PLFA) and toxicological tests with Vibrio fischeri. Injection of nZVI resulted in a rapid decrease in the Cr(VI) and total Cr concentrations in the groundwater without any substantial effect on its chemical properties. The ecotoxicological test with V. fischeri did not indicate any negative changes in the toxicity of the groundwater following the application of nZVI and no significant changes were observed in cultivable psychrophilic bacteria densities and PLFA concentrations in the groundwater samples during the course of the remediation test. However, PLFA of soil samples revealed that the application of nZVI significantly stimulated the growth of Gram-positive bacteria. Principle component analysis (PCA) was applied to the PLFA results for the soil samples from the site in order to explain how Cr(VI) reduction and the presence of Fe influence the indigenous populations. The PCA results clearly indicated a negative correlation between the Cr concentrations and the biota before the application of nZVI and a significant positive correlation between bacteria and the concentration of Fe after the application of nZVI. PMID:24369106

N?me?ek, Jan; Lhotský, Ond?ej; Cajthaml, Tomáš

2014-07-01

192

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

SciTech Connect

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

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

2000-06-01

193

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

PubMed

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

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

2014-01-30

194

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

SciTech Connect

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%.

Lynch, P. L.

1999-01-15

195

Reduction and immobilization of radionuclides and toxic metal ions using combined zero valent iron and anaerobic bacteria. 1998 annual progress report  

SciTech Connect

'Previous research findings indicate that both zero valent iron and sulfate reducing bacteria (SRB) can yield significant decreases in Cr(VI) or U(VI) concentrations due to abiotic and microbial reduction, respectively. The major hypothesis associated with this research project is that a combined abiotic-biological system can synergistically combine both processes to maximize metal ion reduction in an engineered permeable reactive barrier. The overall goal of this project is to design a combined abiotic/microbial, reactive, permeable, in-situ barrier with sufficient reductive potential to prevent downgradient migration of toxic metal ions. The field-scale application of this technology would utilize anaerobic digester sludge, Fe(O) particles for supporting anaerobic biofilms, and suitable aquifer material for construction of the barrier. Successful completion of this goal requires testing of the two hypotheses listed above by evaluating: (1) the rates of abiotic metal ion reduction, and (2) the rates of microbial metal ion reduction in microbial and combined abiotic/microbial reduction systems under a range of environmental conditions. This report summarizes work after one and one-half years of a three year project. Abiotic studies: The thrust of the abiotic research conducted to date has been to determine the rates of Cr(VI) reduction in batch reactors and to evaluate the role of aquifer materials on those rates. Experiments have been conducted to determine the rates of reduction by Fe(II) and Fe(O). The parameters that have been evaluated are the effect of pH and the presence of sulfide and aquifer material.'

Weathers, L.

1998-06-01

196

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

PubMed Central

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

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

2008-01-01

197

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

PubMed

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 50g/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

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

2015-04-01

198

Experimentally determined uranium isotope fractionation during reduction of hexavalent U by bacteria and zero valent iron.  

PubMed

Variations in stable isotope ratios of redox sensitive elements are often used to understand redox processes occurring near the Earth's surface. Presented here are measurements of mass-dependent U isotope fractionation induced by U(VI) reduction by zerovalent iron (Fe0) and bacteria under controlled pH and HCO3- conditions. In abiotic experiments, Fe0 reduced U(VI), but the reaction failed to induce an analytically significant isotopic fractionation. Bacterial reduction experiments using Geobacter sulfurreducens and Anaeromyxobacter dehalogenans reduced dissolved U(VI) and caused enrichment of 238U relative to 235U in the remaining U(VI). Enrichmentfactors (epsilon) calculated using a Rayleigh distillation model are -0.31% per hundred and -0.34% per hundred for G. sulfurreducens and A. dehalogenans, respectively, under identical experimental conditions. Further studies are required to determine the range of possible values for 238U/235U fractionation factors under a variety of experimental conditions before broad application of these results is possible. However, the measurable variations in delta(5238)U show promise as indicators of reduction for future studies of groundwater contamination, geochronology, U ore deposit formation, and U biogeochemical cycling. PMID:17153999

Rademacher, Laura K; Lundstrom, Craig C; Johnson, Thomas M; Sanford, Robert A; Zhao, Juanzho; Zhang, Zhaofeng

2006-11-15

199

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

PubMed

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

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

2014-08-15

200

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

PubMed

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

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

2011-03-01

201

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

SciTech Connect

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.

Zhang, Man [Auburn University, Auburn, Alabama; He, Feng [ORNL; Zhao, Dongye [Auburn University, Auburn, Alabama; Hao, Xiaodi [Beijing University of Civil Engineering and Architecture

2011-01-01

202

A comparison of the low frequency electrical signatures of iron oxide versus calcite precipitation in granular zero valent iron columns  

Microsoft Academic Search

Geophysical methods have been proposed as technologies for non-invasively monitoring geochemical alteration in permeable reactive barriers (PRBs). We conducted column experiments to investigate the effect of mineralogy on the electrical signatures resulting from iron corrosion and mineral precipitation in Fe0 columns using (a) Na2SO4, and (b) NaHCO3 plus CaCl2 mixture, solutions. At the influent interface where the reactions were most

Yuxin Wu; Lee Slater; Roelof Versteeg; Douglas LaBrecque

2008-01-01

203

Incorporation of nanoscale zero-valent iron particles inside the channels of SBA-15 silica rods by a “two solvents” reduction technique  

NASA Astrophysics Data System (ADS)

A new reduction method named a “two solvents” reduction technique was developed for incorporation of nanoscale zero-valent iron particles (NZVIs) inside the channels of SBA-15 silica rods under mild conditions. The resulting NZVIs/SBA-15 composites were compared with the ones prepared by the conventional liquid phase reduction method in structure, morphology and reactivity. All the samples were characterized by X-ray diffraction (XRD), N2 adsorption-desorption isotherms, transmission electron microscopy (TEM) and all-direct-reading plasma atomic emission spectrometry (ICP-AES). Results showed that abundant ultrasmall zero-valent iron particles were synthesized and well dispersed in the mesopores of SBA-15 silica rods by the new reduction technique, whereas larger iron particles were supported and aggregated on the surface of the silica rods by conventional reduction method. Batch experiment demonstrated that NZVIs incorporated inside the silica channels had higher reactivity for the removal of Cr(VI) in aqueous solution than those supported on the surface.

Sun, Xia; Yu, Hongxia; Zheng, Da; Wang, Xuesong; Li, Jiansheng; Wang, Lianjun

2013-08-01

204

A comparison of the low frequency electrical signatures of iron oxide versus calcite precipitation in granular zero valent iron columns  

NASA Astrophysics Data System (ADS)

Geophysical methods have been proposed as technologies for non-invasively monitoring geochemical alteration in permeable reactive barriers (PRBs). We conducted column experiments to investigate the effect of mineralogy on the electrical signatures resulting from iron corrosion and mineral precipitation in Fe 0 columns using (a) Na 2SO 4, and (b) NaHCO 3 plus CaCl 2 mixture, solutions. At the influent interface where the reactions were most severe, a contrasting time-lapse electrical response was observed between the two columns. Solid phase analysis confirmed the formation of corrosion halos and increased mineralogical complexity in the corroded sections of the columns compared to the minimal/non-corroded sections. We attribute the contrasting time-lapse signatures to the differences in the electrical properties of the mineral phases formed within the two columns. While newly precipitated/transformed polarizable and semi-conductive iron oxides (mostly magnetite and green rust) increase the polarization and conductivity of the sulfate column, the decrease of both parameters in the bicarbonate column is attributed to the precipitation of non-polarizable and non-conductive calcite. Our results show that precipitate mineralogy is an important factor influencing the electrical properties of the corroded iron cores and must be considered if electrical geophysical methods are to be developed to monitor PRB barrier corrosion processes in situ.

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

2008-01-01

205

A comparison of the low frequency electrical signatures of iron oxide versus calcite precipitation in granular zero valent iron columns.  

PubMed

Geophysical methods have been proposed as technologies for non-invasively monitoring geochemical alteration in permeable reactive barriers (PRBs). We conducted column experiments to investigate the effect of mineralogy on the electrical signatures resulting from iron corrosion and mineral precipitation in Fe0 columns using (a) Na2SO4, and (b) NaHCO3 plus CaCl2 mixture, solutions. At the influent interface where the reactions were most severe, a contrasting time-lapse electrical response was observed between the two columns. Solid phase analysis confirmed the formation of corrosion halos and increased mineralogical complexity in the corroded sections of the columns compared to the minimal/non-corroded sections. We attribute the contrasting time-lapse signatures to the differences in the electrical properties of the mineral phases formed within the two columns. While newly precipitated/transformed polarizable and semi-conductive iron oxides (mostly magnetite and green rust) increase the polarization and conductivity of the sulfate column, the decrease of both parameters in the bicarbonate column is attributed to the precipitation of non-polarizable and non-conductive calcite. Our results show that precipitate mineralogy is an important factor influencing the electrical properties of the corroded iron cores and must be considered if electrical geophysical methods are to be developed to monitor PRB barrier corrosion processes in situ. PMID:17996979

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

2008-01-28

206

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

NASA Astrophysics Data System (ADS)

The application of nanoscale zero-valent iron (nZVI) for in situ groundwater remediation has received increased attention as a beneficial and novel remediation technique. A precondition for effective nZVI field applications is its delivery to the contaminated source zones. This has proved to be difficult due to the limited mobility of nZVI, which remains one major obstacle to widespread utilization of this remediation approach (O'CAROLL ET AL., 2012). One important factor that controls mobility of nZVI is physical and chemical heterogeneity within the subsurface, such as mineralogical variations (KIM ET AL., 2012). In our previous study we showed that the nZVI transport in carbonate-rich porous media is significantly reduced compared to that in quartz porous media (LAUMANN ET AL., 2012). This is caused by favorable nZVI deposition onto carbonate sand and is attributed to the less negative surface charge of carbonate compared to that of quartz sand under the range of water chemical conditions typically encountered in aquifers. New strategies are therefore required to improve nZVI mobility in carbonate-rich porous media. One approach can be the injection of polyelectrolytes in the subsurface, which are expected to adsorb onto aquifer grains and provide greater repulsion between nZVI and the porous media. In this study the effect of co-injected polyelectrolytes on the transport of polyacrylic acid (PAA) coated nZVI in two model porous media, quartz and carbonate sands was evaluated. Column experiments were carried out aiming to evaluate mobility of PAA-nZVI co-injected with four polyelectrolytes, including natural organic matter (NOM), humic acid, carboxymethyl cellulose (CMC), and lignin sulfonate. The results demonstrated that the co-injection of the chosen polyelectrolytes does not influence mobility of PAA-nZVI in quartz sand; the breakthrough with co-injected polyelectrolytes was similar to that of the pure PAA-nZVI dispersion. This observation can be explained by the strong negative surface charge of the quartz sand, which was apparently not changed in the presence of polyelectrolytes. Conversely, the co-injected polyelectrolytes affected the breakthrough in carbonate sand, increasing nZVI mobility for approximately 15%. This can be explained by the attachment of the polyelectrolytes to the less negatively charged carbonate sand, which then promoted the PAA-nZVI mobility. Even though there are structural differences among the polyelectrolytes applied in this study, our results showed no significant variations in the PAA-nZVI mobility when these polyelectrolytes are present at concentration of 50 mg L-1. Lignin sulfonate was furthermore selected to investigate the effect of different polyelectrolyte concentrations (0, 10, 25, 50, 250, and 500 mg L-1) on the PAA-nZVI mobility. The results showed that higher lignin sulfonate concentrations (250 and 500 mg L-1) do not affect the transport of PAA-nZVI in quartz sand. In carbonate sand, on contrary, increasing mobility due to co-injected lignin sulfonate was observed at concentrations above 25 mg L-1, having the highest value with 500 mg L-1 co-injected with the PAA-nZVI dispersion. Overall, the results demonstrated that lignin sulfonate adsorption onto the carbonate sand reduce PAA-nZVI deposition onto aquifer grains and promote its mobility, the effect which is more pronounced at higher polyelectrolyte concentrations co-injected with the PAA-nZVI dispersion. The project is funded by the Federal Ministry of Agriculture, Forestry, Environment and Water Management (BMLFUW). Management by Kommunalkredit Public Consulting GmbH. Literature O'CAROLL, D. ET AL., (2012): Advances in Water Resources, in press. KIM, H.-J. ET AL., (2012): Journal of Colloid and Interface Science 370, 1-10. LAUMANN, S. ET AL., (2012): Environmental Pollution, submitted.

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

2013-04-01

207

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

NASA Astrophysics Data System (ADS)

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.

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

2013-12-01

208

Application of ultrasound to enhance the zero-valent iron-initiated abiotic degradation of halogenated aliphatic compounds  

NASA Astrophysics Data System (ADS)

Permeable iron barriers, while effective as a near-passive in situ remediation technology for halogenated organic solvents, are susceptible to the loss of reactivity over time, most probably due to a build up of corrosion products or other precipitates on the iron surface. If such material can be removed, a barrier's lifetime can be significantly extended. This proof-of-concept project employed ultrasonic energy to rejuvenate an iron surface. Through batch studies, iron's capacity to degrade dissolved chlorinated solvents under various conditions before and after sonication was examined. The impact of iron pretreatment, groundwater quality, and sonication and the nature of the deposits formed on iron during solvent degradation were determined in order to evaluate the physical mechanism of ultrasonic enhancement of iron and to develop guidelines for barrier design and an ultrasound delivery system for a future field study. Iron (coarse filings, 100-mesh powder, or foamed pellets) placed in deoxygenated natural groundwater was exposed to 330 W-hr of ultrasonic energy prior to the introduction of trichloroethylene (TCE). The iron was also subjected to various pretreatments to create surface conditions with differing rates of activity for chlorinated solvent degradation. Aqueous concentrations of TCE and any degradation products were monitored over time. Geochemical modeling indicated that an iron barrier in this water would be subject to heavy precipitation of carbonates and hydroxides. Sonication positively impacted iron's degradation of chlorinated solvents, probably most directly linked to an increase in active specific surface area, achieved by removing deposits and/or etching the surface, as suggested by scanning electron micrographs. X-Ray photoelectron spectroscopy (XPS) analysis indicated that sonication also changes the chemical composition of the outermost 40 Angstroms of an iron surface. For some degraded irons, activity was restored to near initial rates after sonication. The nonchlorinated fraction of degradation products increased after sonication, suggesting more complete, as well as more rapid, degradation. The application of ultrasound to restore an iron barrier holds great promise. Sonication removes obstructive material from an iron surface, improves its activity for the degradation of chlorinated solvents, and is effective even in water environments with a great tendency to form precipitates.

Ruiz, Nancy Elaine

209

Effects on nano zero-valent iron reactivity of interactions between hardness, alkalinity, and natural organic matter in reverse osmosis concentrate.  

PubMed

Nanoscale zero-valent iron (NZVI) is considered to have potential to reduce nitrate in the concentrate generated by high pressure membrane processes aimed at water reuse. However, it is necessary to verify the effect of the matrix components in the concentrates on NZVI reactivity. In this study, the influence of hardness, alkalinity, and organic matter on NZVI reactivity was evaluated by the response surface method (RSM). Hardness (Ca2+) had a positive effect on NZVI reactivity by accelerating iron corrosion. In contrast, alkalinity (bicarbonate; HCO-3) and organic matter (humic acid; HA) had negative effects on NZVI reactivity due to morphological change to carbonate green rust, and to competitive adsorption of HA, respectively. The validity of the statistical prediction model derived from RSM was confirmed by an additional confirmation experiment, and the experimental result was within the 95% confidential interval. Therefore, it can be indicated that the RSM model produced results that were statistically significant. PMID:24552045

Hwang, Yuhoon; Shin, Hang-Sik

2013-11-01

210

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...

211

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

PubMed

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

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

2015-05-01

212

Effects of humic acid on arsenic(V) removal by zero-valent iron from groundwater with special references to corrosion products analyses.  

PubMed

The effects of humic acid (HA) on As(V) removal by zero-valent iron (Fe(0)) from groundwater, associated with corrosion products analyses, were investigated using batch experiments. It was found that arsenic was rapidly removed from groundwater possibly due to its adsorption and co-precipitation with the corrosion products of Fe(0). The removal rate of arsenic by Fe(0) was inhibited in the presence of HA probably because of the formation of soluble Fe-humate in groundwater which hindered the production of iron precipitates. A longer reaction time was then required for arsenic removal. Such an influence of HA on arsenic removal increased with increasing HA concentration from 5 to 25mgL(-1). The binding capacity of HA for dissolved Fe was estimated to be about 0.75mg Femg(-1) HA. When the complexation of HA with dissolved Fe was saturated, further corrosion of Fe(0) would produce precipitates, which significantly accelerated the removal of arsenic from groundwater via adsorption and co-precipitation with the corrosion products. Iron (hydr)oxides such as maghemite, lepidocrocite, and magnetite were characterized by XRD analyses as the corrosion products, while As(V) was found on the surface of these corrosion products as detected by fourier transform infrared spectrometry and X-ray photoelectron spectroscopy. PMID:19157491

Rao, Pinhua; Mak, Mark S H; Liu, Tongzhou; Lai, Keith C K; Lo, Irene M C

2009-04-01

213

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

PubMed

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

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

2013-01-01

214

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

PubMed

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

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

2014-12-15

215

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

PubMed

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. PMID:20813426

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

2010-11-25

216

Removal of chromium (VI) by acid-washed zero-valent iron under various groundwater geochemistry conditions.  

PubMed

The hexavalent chromium (Cr(VI)) removal capacity of acid-washed zerovalent iron (AW-Fe0) was evaluated under different groundwater geochemistry conditions through column experiments. It was found that each gram of the AW-Fe0 could remove 0.65-1.76 mg of Cr(VI) from synthetic groundwater in the absence of bicarbonate (HCO3-), magnesium and/or calcium ions. Groundwater geochemistry was found to exert various degrees of impact on Cr(VI) removal by the AW-Fe0, in which HCO3- alone gave the mildest impact whereas the copresence of calcium and HCO3- exerted the greatest impact In comparison with the unwashed Fe0, the AW-Fe0 showed a poorer Cr(VI) removal capacity and was also more susceptible to the influence of the dissolved groundwater constituents on Cr(VI) removal,thereby indicating the unsuitability of using AW-Fe0 in permeable reactive barriers for remediation of Cr(VI)-contaminated groundwater. On the AW-Fe0 surface, where the indigenous iron precipitates were almost erased, trivalent chromium including chromium (III) oxides, hydroxides, and oxyhydroxides in irregular strip, chick footmark-liked or boulder-liked forms as well as Cr(III)-Cr(VI) mixed oxides were detected. PMID:18351099

Lai, Keith C K; Lo, Irene M C

2008-02-15

217

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

NASA Astrophysics Data System (ADS)

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.

Kesavan, Sathees Kumar

218

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

PubMed Central

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

Xu, Lejin; Wang, Jianlong

2013-01-01

219

Molecular Stress Responses to Nano-Sized Zero-Valent Iron (nZVI) Particles in the Soil Bacterium Pseudomonas stutzeri  

PubMed Central

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

Saccà, Maria Ludovica; Fajardo, Carmen; Martinez-Gomariz, Montserrat; Costa, Gonzalo; Nande, Mar; Martin, Margarita

2014-01-01

220

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

PubMed

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

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

221

Examination of Cr(VI) treatment by zero-valent iron using in situ, real-time X-ray absorption spectroscopy and Cr isotope measurements  

NASA Astrophysics Data System (ADS)

A series of replicate flow-through cell experiments was conducted to characterize Cr isotope fractionation during Cr(VI) treatment by granular zero-valent iron (ZVI). Synthetic groundwater containing 50 mg L-1 Cr(VI) was pumped upward through a custom-made cell packed with ZVI under anaerobic conditions. The geochemical evolution of the system was monitored using pH and redox measurements, while aqueous effluent samples were retained for analysis of cations and Cr isotopes. Real-time, in situ X-ray absorption near edge structure (XANES) spectroscopy collected via a Kapton® window in the cell provided additional information on the speciation of the reaction products. Increases in ?53Cr values corresponding to decreases in Cr(VI) concentration suggested the occurrence of redox processes. Spectroscopic results correlated well with the isotope data, indicating reduction of Cr(VI) to Cr(III). The isotope data did not appear to follow a single trend. A two-stage system was proposed to explain the complex isotope trend, where the rapid Cr removal was associated with very little fractionation (? = -0.2‰), whereas slower removal was associated with a greater degree of fractionation (? = -1.2‰ to -1.5‰). Reactive transport modeling was used to quantify distinct isotope fractionation values (?), differentiated by a significant change in the Cr removal rate.

Jamieson-Hanes, Julia H.; Lentz, Adam M.; Amos, Richard T.; Ptacek, Carol J.; Blowes, David W.

2014-10-01

222

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

PubMed

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

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

2015-03-01

223

SBA-15-incorporated nanoscale zero-valent iron particles for chromium(VI) removal from groundwater: mechanism, effect of pH, humic acid and sustained reactivity.  

PubMed

Nanoscale zero-valent iron particles (NZVIs) were incorporated inside the channels of SBA-15 rods by a "two solvents" reduction technique and used to remove Cr(VI) from groundwater. The resulting NZVIs/SBA-15 composites before and after reaction were characterized by N2 adsorption/desorption, X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). Results helped to propose the mechanism of Cr(VI) removal by NZVIs/SBA-15, where Cr(VI) in aqueous was firstly impregnated into the channels of the silica, then adsorbed on the surfaces of the incorporated NZVIs and reduced to Cr(III) directly in the inner pores of the silica. Corrosion products included Fe2O3, FeO(OH), Fe3O4 and Cr2FeO4. Batch experiments revealed that Cr(VI) removal decreased from 99.7% to 92.8% when the initial solution pH increased from 5.5 to 9.0, accompanied by the decrease of the kobs from 0.600 to 0.024 min(-1). Humic acid (HA) had a little effect on the removal efficiency of Cr(VI) by NZVIs/SBA-15 but could decrease the reduction rate. The stable reduction of NZVIs/SBA-15 was observed within six cycles. NZVIs/SBA-15 composites offer a promising alternative material to remove heavy metals from groundwater. PMID:24374562

Sun, Xia; Yan, Yubo; Li, Jiansheng; Han, Weiqing; Wang, Lianjun

2014-02-15

224

[Effects of particle size of zero-valent iron on the reactivity of activating persulfate and kinetics for the degradation of acid orange 7].  

PubMed

This research described the heterogeneous reactions of persulfate with different particle sizes of zero-valent iron (including 1 mm-ZVI,150 ?m-ZVI,50 nm-ZVI) for degradation of acid orange 7(AO7) , and studied the kinetics and intermediate products of AO7 under these systems. The results demonstrated that these three types of ZVI were efficient in promoting the degradation of AO7, the degradation efficiencies of AO7 were 43% , 97% , and 100% within 90 min respectively, in the 1 mm-ZVI,150 ?m-ZVI and 50 nm- ZVI systems, respectively. With the results of kinetic fitting models, the pseudo first-order kinetics exhibited better fitting results in the 1 mm-ZVI,150 ?m-ZVI systems, while the second-order kinetics exhibited better fitting results in the 50 nm-ZVI system. And the different ZVI types exhibited difference on the AO7 degradation rate constant, which ranged as 50 nm-ZVI > 150 ?m-ZVI > 1 mm-ZVI. The iron corrosion products coating on the ZVI after reaction were composed of ?-Fe2 O3 and some Fe3O4 in the 1 mm-ZVI system while that consisted of Fe3O4 and ?-Fe2O3, FeOOH respectively, in thel50 ?m-ZVI and 50 nm-ZVI systems,. Which were identified by scanning electron microscope (SEM) with energy dispersive spectrometer (EDS) and Raman spectroscopy. Some intermediate products, including 2-naphthalenol, 2-methylphenol, 4-ethyl- 3-methyl-phenol, isoindole- 1,3-dione and phthalic acid et al. were identified by GC/MS measurement. Both UV-vis absorbance spectra and GC/MS determination indicated that there was difference in degradation paths of AO7 between the three systems. PMID:25518660

Li, Huan-xuan; Wan, Jin-quan; Ma, Yong-wen; Huang, Ming-zhiz; Wang, Yan; Chen Yang, Mei

2014-09-01

225

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)

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.

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

226

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

PubMed

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

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

2013-06-01

227

Organic-coated nanoparticulate zero valent iron for remediation of chemical oxygen demand (COD) and dissolved metals from tropical landfill leachate.  

PubMed

The use of nanoparticulate zero valent iron (NZVI) in the treatment of inorganic contaminants in landfill leachate and polluted plumes has been the subject of many studies, especially in temperate, developed countries. However, NZVI's potential for reduction of chemical oxygen demand (COD) and treatment of metal ion mixtures has not been explored in detail. We investigated the efficiency of NZVI synthesized in the presence of starch, mercaptoacetic, mercaptosuccinic, or mercaptopropenoic acid for the reduction of COD, nutrients, and metal ions from landfill leachate in tropical Sri Lanka. Synthesized NZVI were characterized with X-ray diffraction (XRD), transmission electron microscopy, X-ray photoelectron spectroscopy, scanning electron microscopy (SEM), thermal gravimetric analysis, Fourier transform infrared spectroscopy (FTIR) and Brunauer-Emmett-Teller. Of the samples tested, Starch-NZVI (S-NZVI) and mercaptoacetic-NZVI (MA-NZVI) performed well for treatment both COD and metal mixture. The removal percentages for COD, nitrate-nitrogen, and phosphate from S-NZVI were 50, 88, and 99 %, respectively. Heavy metal removal was higher in S-NZVI (>95 %) than others. MA-NZVI, its oxidation products, and functional groups of its coating showed the maximum removal amounts for both Cu (56.27 mg g(-1)) and Zn (28.38 mg g(-1)). All mercapto-NZVI showed well-stabilized nature under FTIR and XRD investigations. Therefore, we suggest mercapto acids as better agents to enhance the air stability for NZVI since chemically bonded thiol and carbonyl groups actively participation for stabilization process. PMID:24535668

Wijesekara, S S R M D H R; Basnayake, B F A; Vithanage, Meththika

2014-06-01

228

Effects of physicochemical factors on Cr(VI) removal from leachate by zero-valent iron and alpha-Fe(2)O(3) nanoparticles.  

PubMed

The effects of nanoparticle dosage, initial hexavalent chromium concentration, pH value, reaction temperature, and initial concentration of humic acid (HA) on chromate (CrO(4)(2-)) removal from landfill leachate by nanoscale zero-valent iron (NZVI) and hematite (alpha-Fe(2)O(3)) nanoparticles were examined in the present investigations. The Cr(VI) removal rate decreased as the initial Cr(VI) concentration and the reaction temperature increased, whereas corresponding removal rate by NZVI was higher than that of alpha-Fe(2)O(3). The optimum pH for the removal of Cr(VI) by NZVI was found to be 5.0 and more than 99.0% of Cr(VI) was removed within 5 h. However, the removal rate by alpha-Fe(2)O(3) decreased as pH increased. Presence of HA resulted in substantial reduction in the rate and extent of Cr(VI) removal by NZVI, whereas Cr(VI) removal rate by alpha-Fe(2)O(3) did not significantly decrease as HA concentration increased from 0.5 g/L to 3.0 g/L. Increasing the dosage of nanoparticles enhanced the rate constant and the removal of Cr(VI) by NZVI and alpha-Fe(2)O(3) followed pseudo-first-order reaction kinetics. The information should be very useful for the successful application of NZVI and alpha-Fe(2)O(3) for the treatment of groundwater or raw wastewater. PMID:20489248

Liu, T Y; Zhao, L; Tan, X; Liu, S J; Li, J J; Qi, Y; Mao, G Z

2010-01-01

229

Mg(OH)2 Supported Nanoscale Zero Valent Iron Enhancing the Removal of Pb(II) from Aqueous Solution.  

PubMed

In this article, a novel composite (Mg(OH)2 supported nanoscale zerovalent iron (denoted as nZVI@Mg(OH)2) was prepared and characterized by X-ray diffraction, scanning electron microscopy, and transmission electron microscopy method. The morphology analysis revealed that Mg(OH)2 appeared as self-supported flower-like spheres, and nano Fe(0) particles were uniformly immobilized on the surface of their "flower petals", thus aggregation of Fe(0) particles was minimized. Then the Pb(II) removal performance was tested by batch experiments. The composite presented exceptional removal capacity (1986.6 mg/g) compared with Mg(OH)2 and nanoscale zerovalent iron due to the synergistic effect. Mechanisms were also explored by a comparative study of the phase, morphology, and surface valence state of composite before and after reaction, indicating that at least three paths are involved in the synergistic removal process: (1) Pb(II) adsorption by Mg(OH)2 (companied with ion exchange reaction); (2) Pb(II) reduction to Pb(0) by nanoscale zerovalent iron; and (3) Pb(II) precipitation as Pb(OH)2. The hydroxies provided by Mg(OH)2 can dramatically promote the role of nanoscale zerovalent iron as reducer, thus greatly enhancing the whole Pb(II) sequestration process. The excellent performance shown in our research potentially provides an alternative technique for Pb(II) pollution treatment. PMID:25826707

Liu, Minghui; Wang, Yonghao; Chen, Luntai; Zhang, Yan; Lin, Zhang

2015-04-22

230

Degradation of chlorobenzene by Fenton?like processes using zero?valent iron in the presence of Fe and Cu  

Microsoft Academic Search

Batch and column tests were conducted to compare the efficiencies of three Fenton?like systems in the degradation of chlorobenzene. In the investigated systems, iron powder was the source of Fe ions, and either Fe or Cu were added in order to enhance the degradation process. Optimum pH and concentrations of Fe, Cu and hydrogen peroxide were assessed by treating synthetic

Michele Pagano; Angela Volpe; Antonio Lopez; Giuseppe Mascolo; Ruggiero Ciannarella

2011-01-01

231

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...

232

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...

233

Removal of co-present chromate and arsenate by zero-valent iron in groundwater with humic acid and bicarbonate.  

PubMed

The interactions of co-present Cr(VI) and As(V), and the influences of humic acid and bicarbonate in the process of Cr(VI) and As(V) removal by Fe(0) were investigated in a batch setting using simulated groundwater with 5 mM NaCl, 1 mM Na(2)SO(4), and 0.8 mM CaCl(2) as background electrolytes at an initial pH value of 7. Cr(VI) and As(V) were observed to be subject to different impacts induced by co-existing As(V) or Cr(VI), humic acid and bicarbonate, originating from their distinct removal mechanisms by Fe(0). Cr(VI) removal is a reduction-dominated process, whereas As(V) removal principally involves adsorption onto iron corrosion products. Experimental results showed that Cr(VI) removal was not affected by the presence of As(V) and humic acid. However, As(V) removal appeared to be inhibited by co-present Cr(VI). When the Cr(VI) concentration was 2, 5, and 10 mg/L, in the absence of humic acid and bicarbonate, As(V) removal rate constants were decreased by 27.9%, 49.0%, and 61.2%, respectively, which probably resulted from competition between Cr(VI) and As(V) for adsorption sites of the iron corrosion products. Furthermore, the presence of humic acid significantly varied As(V) removal kinetics by delaying the formation and aggregation of iron hydroxides due to the formation of soluble Fe-humate complexes and stably dispersed fine iron hydroxides colloids. In the presence of bicarbonate, both Cr(VI) and As(V) removal was increased and the inhibitory effect of Cr(VI) on As(V) removal was suppressed, resulting from the buffering effects and the promoted iron corrosion induced by bicarbonate, and the formation of CaCO(3) in solution, which enhanced As(V) adsorption. PMID:19321187

Liu, Tongzhou; Rao, Pinhua; Mak, Mark S H; Wang, Peng; Lo, Irene M C

2009-05-01

234

Zero-valent iron reduction of nitrate in the presence of ultraviolet light, organic matter and hydrogen peroxide  

Microsoft Academic Search

This paper describes the use of metallic iron (Fe0) powder for nitrate removal in a well-mixed batch reactor. Important variables explored include Fe0 dosage (1–3g\\/L), UV light intensity (64–128W), and the presence of propanol (20mg\\/L as DOC) and H2O2 (100–200mg\\/L). Accumulation of ferrous ions released from the Fe0 surface can be expressed by an S-curve, which involves lag growth phase,

Chih-Hsiang Liao; Shyh-Fang Kang; Yu-Wei Hsu

2003-01-01

235

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

PubMed

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

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

2012-07-25

236

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)

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.

Ahn, J.; Kim, C.; Huynh, T. N.; Hwang, I.

2013-12-01

237

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

PubMed

The effect of precipitates on the reactivity of iron metal (Fe0) with 1,1,1-trichloroethane (TCA) was studied in batch systems designed to model groundwaters that contain dissolved carbonate species (i.e., C(IV)). At representative concentrations for high-C(IV) groundwaters (approximately 10(-2) M), the pH in batch reactors containing Fe0 was effectively buffered until most of the aqueous C(IV) precipitated. The precipitate was mainly FeCO3 (siderite) but may also have included some carbonate green rust. Exposure of the Fe0 to dissolved C(IV) accelerated reduction of TCA, and the products formed under these conditions consisted mainly of ethane and ethene, with minor amounts of several butenes. The kinetics of TCA reduction were first-order when C(IV)-enhanced corrosion predominated but showed mixed-order kinetics (zero- and first-order) in experiments performed with passivated Fe0 (i.e., before the onset of pitting corrosion and after repassivation by precipitation of FeCO3). All these data were described by fitting a Michaelis-Menten-type kinetic model and approximating the first-order rate constant as the ratio of the maximum reaction rate (Vm) and the concentration of TCA at half of the maximum rate (K(1/2)). The decrease in Vm/K(1/2) with increasing C(IV) exposure time was fit to a heuristic model assuming proportionality between changes in TCA reduction rate and changes in surface coverage with FeCO3. PMID:12387405

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

2002-10-15

238

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

NASA Astrophysics Data System (ADS)

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.

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

2010-05-01

239

Influence of various organic molecules on the reduction of hexavalent chromium mediated by zero-valent iron.  

PubMed

Hexavalent chromium is a priority pollutant in many countries. Reduction of Cr(VI) to Cr(III) is desirable as the latter specie is an essential nutrient for maintaining normal physiological function and also has a low mobility and bioavailability. A variety of naturally-occurring organic molecules (containing alpha-hydroxyl carbonyl, alpha-hydroxyl carboxylate, alpha-carbonyl carboxylate, phenolate, carboxylates and/or thiol groups, siderophore, ascorbic acid); chelating agents (ethylenediaminetetraacetic acid derivates, acetyacetone) and others were examined their reducing activity towards a surfactant preparation (Tween 20) containing Cr(VI) and Fe(0) under a variety of reaction conditions. An appreciable enhancement (up to 50-fold) of the pseudo-first-order rate constant was achieved at acidic and circum neutral pH values for those compounds capable of reducing Cr(VI) (alpha-hydroxyl carboxylate, ascorbic acid, cysteine). Comparable enhancements were obtained for certain chelating agents (ethylenediaminetetraacetic acid derivates and siderophores) which is attributed to the formation of complexes with reaction products, such as Cr(III) and Fe(III), which impede the precipitation of Cr(III) and Fe(III) hydroxides and Cr(x)Fe(1-)(x)(OH)(3) and thus reduce passivation of the Fe(0) surface. The results suggest that these molecules might be used in effective remediation mediated by Fe(0) of Cr(VI)-contaminated soils or groundwater in a wide range of pH, thus increasing reaction rates and long-term performance of permeable reductive barriers. PMID:19559460

Rivero-Huguet, Mario; Marshall, William D

2009-08-01

240

The Use of Ultrasound to Restore the Dehalogenation Activity of Iron in Permeable Reactive Barriers  

Microsoft Academic Search

In situ permeable reactive barriers (PRBs) containing iron as the reactive agent have gained popularity in the past decade as a near-passive, in situ groundwater remediation technology for halogenated solvents. Although zero-valent iron has been shown to be effective for this purpose, a continuing problem is the loss of system reactivity over time. This loss is due, at least in

Cherie L. Geiger; Christian A. Clausen; Debra R. Reinhart; Nancy Ruiz

241

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...

242

Reduction of TNT and RDX by Core Material from an Iron Permeable Reactive Barrier  

Microsoft Academic Search

We recently completed a pilot-scale permeable reactive barrier (PRB) with zero-valent iron (ZVI) to treat groundwater contaminated with explosives (TNT and RDX) at the Cornhusker Army Ammunition Plant (CAAP) near Grand Island, Nebraska. While the PRB at CAAP continues to be effective at removing explosives from the groundwater, the hydraulic performance is significantly reduced. This may be due to the

James T. Nurmi; Paul G. Tratnyek; Richard L. Johnson; R. Brad Thoms; Reid O'Brien Johnson

243

Reductive dechlorination of TCE by zero valent bimetals.  

PubMed

Six zero valent bimetal combinations were tested for trichloroethene (TCE) dechlorination. Palladium, nickel, and copper were coated at 500 mg kg(-1) or less onto zero valent iron, producing Pd/Fe, Ni/Fe, and Cu/Fe bimetals, and zinc, producing Pd/Zn, Ni/Zn, and Cu/Zn bimetals. The order of reactivity of the six bimetals and two metals based on surface area normalized pseudo first order rate constants was observed to be: Pd/Fe > Pd/Zn > Ni/Fe > Cu/Fe > Ni/Zn > Cu/Zn > Fe > Zn. Thus, in general, 1) iron metal and bimetals exhibit faster reaction rates than the corresponding zinc reductants, 2) bimetals exhibit faster reaction rates than pure metals, and 3) metal coating enhance reactivity in the order of Pd > Ni > Cu. Chlorinated intermediate products were observed in small amounts for Fe only. In all cases, the chloride balance, calculated from TCE and chloride concentrations, ranged from 90 to 111%. The results are discussed in terms of the effects of bimetal combinations on catalytic dechlorination, prevention of nonreactive film and metal corrosion. PMID:12641254

Kim, Y H; Carraway, E R

2003-01-01

244

Degradation of Toxic Chemicals by Zero-Valent Metal Nanoparticles - A Literature Review  

Microsoft Academic Search

The ultimate aim of researchers in the area of decontamination is to develop the perfect decontaminant - a substance that will degrade all contaminants but will leave surfaces and environments unharmed. Published research into zero-valent metal particles (ZVMs), in particular iron, shows that these particles, particularly those whose size is on the nanoscale, have the potential to be used as

Lyndal McDowall

245

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...

246

Reductive dechlorination of octachlorodibenzo-p-dioxin by nanosized zero-valent zinc: modeling of rate kinetics and congener profile.  

PubMed

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

Bokare, Varima; Jung, Ju-Lim; Chang, Yoon-Young; Chang, Yoon-Seok

2013-04-15

247

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 ...

248

Oxidative degradation of organic pollutants in aqueous solution using zero valent copper under aerobic atmosphere condition.  

PubMed

Oxidative degradation of organic pollutants and its mechanism were investigated in aqueous solution using zero valent copper (ZVC) under aerobic atmosphere condition. Diethyl phthalate (DEP) was completely oxidized after 120 min reaction by ZVC at initial pH 2.5 open to the air. DEP degradation followed the pseudo-first-order kinetics after the lag period, and the degradation rate of DEP increased gradually with the increase of ZVC dosage, and the decrease of initial pH from 5.8 to 2.0. ZVC required a shorter induction time and exhibited persistent oxidation capacity compared to that of zero valent iron and zero valent aluminium. The mechanism investigation showed that remarkable amount of Cu(+)/Cu(2+) and H2O2 were formed in ZVC acidic system, which was due to the corrosive dissolution of ZVC and the concurrent reduction of oxygen. The addition of tert-butanol completely inhibited the degradation of DEP and the addition of Fe(2+) greatly enhanced the degradation rate, which demonstrated that hydroxyl radical was mainly responsible for the degradation of DEP in ZVC acidic system under aerobic atmosphere condition, and the formation of hydroxyl radical was attributed to the Fenton-like reaction of in situ formed Cu(+) with H2O2. PMID:24857902

Wen, Gang; Wang, Sheng-Jun; Ma, Jun; Huang, Ting-Lin; Liu, Zheng-Qian; Zhao, Lei; Xu, Jin-Lan

2014-06-30

249

Carbon isotope fractionation during reductive dechlorination of TCE in batch experiments with iron samples from reactive barriers.  

PubMed

Reductive dechlorination of trichloroethene (TCE) by zero-valent iron produces a systematic enrichment of 13C in the remaining substrate that can be described using a Rayleigh model. In this study, fractionation factors for TCE dechlorination with iron samples from two permeable reactive barriers (PRBs) were established in batch experiments. Samples included original unused iron as well as material from a barrier in Belfast after almost 4 years of operation. Despite the variety of samples, carbon isotope fractionations of TCE were remarkably similar and seemed to be independent of iron origin, reaction rate, and formation of precipitates on the iron surfaces. The average enrichment factor for all experiments was -10.1 per thousand (+/- 0.4 per thousand). These results indicate that the enrichment factor provides a powerful tool to monitor the reaction progress, and thus the performance, of an iron-reactive barrier over time. The strong fractionation observed may also serve as a tool to distinguish between insufficient residence time in the wall and a possible bypassing of the wall by the plume, which should result in an unchanged isotopic signature of the TCE. Although further work is necessary to apply this stable isotope method in the field, it has potential to serve as a unique monitoring tool for PRBs based on zero-valent iron. PMID:14516939

Schüth, Christoph; Bill, Markus; Barth, Johannes A C; Slater, Gregory F; Kalin, Robert M

2003-10-01

250

Geochemistry and Performance of Permeable Reactive Barriers  

Microsoft Academic Search

The application of permeable reactive barrier (PRB) systems for treatment of contaminated groundwater has increased progressively over the past ten years. Since the initial installations in the early 1990's many PRB systems containing zero valent iron have functioned as designed. Treatment levels that do not meet design objectives are generally attributable to discrepancies between predicted and observed contaminant distribution and

D. Blowes; C. J. Ptacek; D. J. Smyth

2001-01-01

251

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...

252

Evaluation of five strategies to limit the impact of fouling in permeable reactive barriers  

Microsoft Academic Search

Ground water flow and geochemical reactive transport models were used to assess the effectiveness of five strategies used to limit fouling and to enhance the long-term hydraulic behavior of continuous-wall permeable reactive barriers (PRBs) employing granular zero valent iron (ZVI). The flow model accounted for geological heterogeneity and the reactive transport model included a geochemical algorithm for simulating iron corrosion

Lin Li; Craig H. Benson

2010-01-01

253

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...

254

Accumulation Rate of Microbial Biomass at Two Permeable Reactive Barrier Sites  

Microsoft Academic Search

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 and permeability. Results are presented from solid phase and groundwater monitoring studies conducted at two Permeable Reactive Barrier sites, U.S. Coast Guard

R. Wilkin; G. Sewell; R. Puls

2001-01-01

255

Effect of various inorganic anions on the degradation of Congo Red, a di azo dye, by the photo-assisted Fenton process using zero-valent metallic iron as a catalyst  

Microsoft Academic Search

The present research focuses on the heterogeneous advanced photo-Fenton processes of the type Fe\\/H2O2\\/UV and Fe\\/ammonium persulfate (APS)\\/UV as a potential technique to degrade Congo Red (di azo dye). Both the oxidants H2O2 and APS showed comparable efficiencies on the iron surface for the mineralization of Congo Red (CR) under UV light. The influence of various reaction parameters like pH

L. Gomathi Devi; S. Girish Kumar; K. Mohan Reddy; C. Munikrishnappa

2009-01-01

256

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

Microsoft Academic Search

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

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

2006-01-01

257

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...

258

Stability of Multi-Permeable Reactive Barriers for Long Term Removal of Mixed Contaminants  

Microsoft Academic Search

The Permeable Reactive Barriers (PRBs) are relatively simple, promising technology for groundwater remediation. A PRBs consisting\\u000a of two reactive barriers (zero valent iron-barrier and bio-barrier) were designed to evaluate the application and feasibility\\u000a of the barriers for the removal of wide range of pollutants from synthetic water. After 470 days of Multi-PRBs column operation,\\u000a the pH level in the water sample

Jai-Young LeeKui-Jae; Kui-Jae Lee; Sun Young Youm; Mi-Ran Lee; Seralathan Kamala-Kannan; Byung-Taek Oh

2010-01-01

259

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...

260

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...

261

Degradation of organic and inorganic contaminants by zero valent iron  

E-print Network

/Feo. The only product observed in the reduction of 2,4-DNT was 2,4-diaminotoluene (2,4-DAT). The 2,4-DAT produced accounted for 83-100% and only 42-54% of the initial mass of 2@4.DNT under anaerobic and aerobic conditions respectively. Since no degradation of 2...

Malla, Deepak Babu

1997-01-01

262

HEXAHYDRO-1,3,5-TRINITRO-1,3,5-TRIAZINE (RDX) DEGRADATION IN BIOLOGICALLY-ACTIVE IRON COLUMNS  

E-print Network

, permeable reactive barrier, RDX, zero-valent iron 1. Introduction RDX (hexahydro-1,3,5-trinitro-1: 319/335-5660) Abstract. Flow-through columns were used to evaluate the efficacy of permeable reactive, there has been an explosion of activity directed at the development and implementation of permeable reactive

Alvarez, Pedro J.

263

Stability of multi-permeable reactive barriers for long term removal of mixed contaminants.  

PubMed

The Permeable Reactive Barriers (PRBs) are relatively simple, promising technology for groundwater remediation. A PRBs consisting of two reactive barriers (zero valent iron-barrier and bio-barrier) were designed to evaluate the application and feasibility of the barriers for the removal of wide range of pollutants from synthetic water. After 470 days of Multi-PRBs column operation, the pH level in the water sample is increased from 4 to 7, whereas the oxidation reduction potential (ORP) is decreased to -180 mV. Trichloroethylene (TCE), heavy metals, and nitrate were completely removed in the zero valent iron-barrier. Ammonium produced during nitrate reduction is removed in the biologically reactive zone of the column. The results of the present study suggest that Multi-PRBs system is an effective alternate method to confine wide range of pollutants from contaminated groundwater. PMID:19949770

Lee, Jai-Young; Lee, Kui-Jae; Youm, Sun Young; Lee, Mi-Ran; Kamala-Kannan, Seralathan; Oh, Byung-Taek

2010-02-01

264

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

NASA Astrophysics Data System (ADS)

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.

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

2010-12-01

265

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

SciTech Connect

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.

Watson, D.B.

2003-12-30

266

Reactive transport modeling of an in situ reactive barrier for the treatment of hexavalent chromium and trichloroethylene in groundwater  

Microsoft Academic Search

Multicomponent reactive transport modeling was conducted for the permeable reactive barrier at the Coast Guard Support Center near Elizabeth City, North Carolina. The zero-valent iron barrier was installed to treat groundwater contaminated by hexavalent chromium and chlorinated solvents. The simulations were performed using the reactive transport model MIN3P, applied to an existing site-specific conceptual model. Reaction processes controlling the geochemical

K. Ulrich Mayer; David W. Blowes; Emil O. Frind

2001-01-01

267

Electro-enhanced Permeable Reactive Barrier : Optimal Design of PRB System With External Current for Effective TCE Removal From Groundwater  

Microsoft Academic Search

The objective of this study was to design an optimal electro-enhanced permeable reactive barrier (E2PRB) system for remediation of trichloroethylene (TCE)-contaminated water using zero valent iron (ZVI) and direct current (DC). A series of column experiments were conducted to evaluate the location of Fe0 permeable reactive barrier (PRB) and the effects of electrode arrangement in the column on the TCE

J. Moon; H. Moon; Y. Roh; H. Kim; Y. Song

2002-01-01

268

Zero-Valent Metallic Treatment System and Its Application for Removal and Remediation of Polychlorinated Biphenyls (Pcbs)  

NASA Technical Reports Server (NTRS)

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.

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

2012-01-01

269

Chemistry and Microbiology of Permeable Reactive Barriers for In Situ Groundwater Clean up  

Microsoft Academic Search

Permeable reactive barriers (PRBs) are receiving a great deal of attention as an innovative, cost-effective technology for in situ clean up of groundwater contamination. A wide variety of materials are being proposed for use in PRBs, including zero-valent metals (e.g., iron metal), humic materials, oxides, surfactant-modified zeolites (SMZs), and oxygen- and nitrate-releasing compounds. PRB materials remove dissolved groundwater contaminants by

Michelle M. Scherer; Sascha Richter; Richard L. Valentine; Pedro J. J. Alvarez

2000-01-01

270

Field Monitoring of a Permeable Reactive Barrier for Removal of Chlorinated Organics  

Microsoft Academic Search

The application of zero-valent iron Fe0 in the funnel-and-gate permeable reactive barrier PRB installed at the Vapokon site, Denmark, was conducted in 1999 to remediate the groundwater contaminated by chlorinated aliphatic hydrocarbons CAHs. Over the past 4 years, except in September 2002 and January 2003, about 92.4-97.5% CAH removal could be achieved with the PRB. Although there was a continuous

Keith C. K. Lai; Irene M. C. Lo; Vibeke Birkelund; Peter Kjeldsen

2009-01-01

271

Laboratory study on sequenced permeable reactive barrier remediation for landfill leachate-contaminated groundwater  

Microsoft Academic Search

Permeable reactive barrier (PRB) was a promising technology for groundwater remediation. Landfill leachate-polluted groundwater riches in various hazardous contaminants. Two lab-scale reactors (reactors A and B) were designed for studying the feasibility of PRB to remedy the landfill leachate-polluted groundwater. Zero valent iron (ZVI) and the mixture of ZVI and zeolites constitute the first section of the reactors A and

Dong Jun; Zhao Yongsheng; Zhang Weihong; Hong Mei

2009-01-01

272

High-density chemical intercalation of zero-valent copper into Bi2Se3 nanoribbons.  

PubMed

A major goal of intercalation chemistry is to intercalate high densities of guest species without disrupting the host lattice. Many intercalant concentrations, however, are limited by the charge of the guest species. Here we have developed a general solution-based chemical method for intercalating extraordinarily high densities of zero-valent copper metal into layered Bi(2)Se(3) nanoribbons. Up to 60 atom % copper (Cu(7.5)Bi(2)Se(3)) can be intercalated with no disruption to the host lattice using a solution disproportionation redox reaction. PMID:22524598

Koski, Kristie J; Cha, Judy J; Reed, Bryan W; Wessells, Colin D; Kong, Desheng; Cui, Yi

2012-05-01

273

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

SciTech Connect

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.

NONE

1999-11-01

274

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

SciTech Connect

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.

Not Available

1999-01-01

275

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

PubMed

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

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

2015-01-01

276

Iron Sulfide as a Sustainable Reactive Material for Permeable Reactive Barriers  

NASA Astrophysics Data System (ADS)

Permeable reactive barriers (PRBs) are gaining acceptance for groundwater remediation, as they operate in situ and do not require continuous energy input. The majority of PRBs use zero-valent iron (ZVI). However, some ZVI PRBs have hydraulically failed [1,2], due to the fact that ZVI may reduce not only contaminants but also water and non-contaminant solutes. These reactions may form precipitates or gas phases that reduce permeability. Therefore, there is a need to assess the hydraulic suitability of possible alternatives, such as iron sulfide (FeS). The capability of FeS to remove both metals and halogenated organics from aqueous systems has been demonstrated previously [3,4], and FeS formed in situ within a ZVI PRB has been linked to contaminant removal [5]. These results suggest possible applications in groundwater remediation as a permeable reactive barrier (PRB) material. However, the propensity of FeS for permeability loss, due to solids and gas production, must be evaluated in order to address its suitability for PRBs. The reduction in permeability for FeS-coated sands under the anoxic conditions often encountered at contaminated groundwater sites was examined through column experiments and geochemical modeling under conditions of high calcium and nitrate, which have been previously shown to cause significant permeability reduction in zero-valent iron (ZVI) systems [6]. The column experiments showed negligible production of both solids and gases. The geochemical model was used to estimate solid and gas volumes generated under conditions of varying FeS concentration. Then, the Kozeny-Carman equation and a power-law relationship was used to predict permeability reduction, with a maximum reduction in permeability of 1% due to solids and about 30% due to gas formation under conditions for which a complete loss of permeability was predicted for ZVI systems. This difference in permeability reduction is driven by the differences in thermodynamic stability of ZVI and FeS in aqueous solutions. The results suggest that geochemical conditions that result in high permeability losses for ZVI systems will necessarily not be problematic, from a permeability perspective, for FeS-based reactive materials. Therefore, this research represents an important advance for sustainable groundwater remediation. References: [1] Mushovic, P., Bartlett, T. R., Morrison, S. (2006) Tech. News & Trends 23, 1-3. [2] Kiilerich, O., Larsen, J. W., Nielsen, C., Deigaard, L. D. (2000) In: Wickramanayake, G.B., et al. (Eds.), Chemical Oxidation and Reactive Barriers: Remediation of Chlorinated and Recalcitrant Compounds, Battelle Press, Columbus, OH, 377-384. [3] Han, Y., Gallegos, T. J., Demond, A. H., Hayes, K. F. (2011) Water Res. 45(2), 593-604. [4] Jeong, H. Y. and Hayes, K. F. (2007) Environ. Sci. Technol. 41(18), 6390-6396. [5] Beak, D. G. and Wilkin, R. T. (2009) J. Contam. Hydrol. 106(1-2), 15-28. [6] Henderson, A. D. and Demond, A. H. (2007) Environ. Eng. Sci. 24(4), 401-423.

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

2012-12-01

277

Zero-valent sulphur is a key intermediate in marine methane oxidation.  

PubMed

Emissions of methane, a potent greenhouse gas, from marine sediments are controlled by anaerobic oxidation of methane coupled primarily to sulphate reduction (AOM). Sulphate-coupled AOM is believed to be mediated by a consortium of methanotrophic archaea (ANME) and sulphate-reducing Deltaproteobacteria but the underlying mechanism has not yet been resolved. Here we show that zero-valent sulphur compounds (S(0)) are formed during AOM through a new pathway for dissimilatory sulphate reduction performed by the methanotrophic archaea. Hence, AOM might not be an obligate syntrophic process but may be carried out by the ANME alone. Furthermore, we show that the produced S(0)--in the form of disulphide--is disproportionated by the Deltaproteobacteria associated with the ANME. Our observations expand the diversity of known microbially mediated sulphur transformations and have significant implications for our understanding of the biogeochemical carbon and sulphur cycles. PMID:23135396

Milucka, Jana; Ferdelman, Timothy G; Polerecky, Lubos; Franzke, Daniela; Wegener, Gunter; Schmid, Markus; Lieberwirth, Ingo; Wagner, Michael; Widdel, Friedrich; Kuypers, Marcel M M

2012-11-22

278

Aerosol synthesis of nano and micro-scale zero valent metal particles from oxide precursors  

SciTech Connect

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.

Phillips, Jonathan [Los Alamos National Laboratory; Luhrs, Claudia [UNM; Lesman, Zayd [UNM; Soliman, Haytham [UNM; Zea, Hugo [UNM

2010-01-01

279

Oxidative removal of bisphenol A using zero valent aluminum-acid system.  

PubMed

Bisphenol A (BPA), a controversial endocrine disruptor, is ubiquitous in the aquatic environment. In this study, the oxidative degradation of BPA and its mechanism using zero valent aluminum (ZVAl)-acid system under air-equilibrated conditions was investigated. Under pH <3.5 acidic conditions, ZVAl demonstrated an excellent capacity to remove BPA. More than 75% of BPA was eliminated within 12 h in pH 1.5 reaction solutions initially containing 4.0 g/L aluminum and 2.0 mg/L BPA at 25 ± 1 °C. The removal of BPA was further accelerated with increasing aluminum loadings. Higher temperature and lower initial pH also facilitated BPA removal. The addition of Fe(2+) into the ZVAl-acid system significantly accelerated the reaction likely due to the enhancing transformation of H(2)O(2) to HO via Fenton reaction. Furthermore, the primary products or intermediates including monohydroxylated BPA, hydroquinone, 2-(4-hydroxyphenyl)propane and 4-isopropenylphenol, were identified and a possible reaction scheme was proposed. The remarkable capacity of the ZVAl-acid system in removing BPA displays its potential application in the treatment of organic compound-contaminated water. PMID:21185583

Liu, Wanpeng; Zhang, Honghua; Cao, Beipei; Lin, Kunde; Gan, Jay

2011-02-01

280

Reaction of zero-valent magnesium with water: Potential applications in environmental remediation  

NASA Astrophysics Data System (ADS)

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.

Lee, Giehyeon; Park, Jaeseon

2013-02-01

281

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...

282

2.2 Zero-valent Iron Nanoparticles 2.2.1 Background  

E-print Network

nanoparticles for the treatment of organic contaminants in groundwater. There are, however, few examples groundwater for almost 20 years (Senzaki and Kumagai 1988) and has been demonstrated in the field, and the removal of arsenic, lead, uranium, mercury, and hexavalent chromium (Nuxoll et al. 2003, Arnold

283

Dechlorination of PCE by mixtures of green rust and zero-valent iron  

E-print Network

in the model is as follows. C~c =CRc ? B (13) where, B is the cumulative aqueous PCE concentration removed by GRsp4. The concentration of PCE removed by GRsp4 at any time was calculated by solving the following equation. dB (k/P)C pcE (CRc B) dt 1/K+ CUE...

Marchal, Fabienne

2002-01-01

284

Aminoclay-templated nanoscale zero-valent iron (nZVI) synthesis for efficient harvesting of  

E-print Network

, micro- algae were successfully collected by attachment to the magnetic rods or by precipitation as a feedstock.6,7 Microalgae-based biorenement entails several downstream processes including cultivation

Mosegaard, Klaus

285

Assessment of polyphenol coated nano zero valent iron for hexavalent chromium removal from contaminated waters.  

PubMed

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

Mystrioti, C; Sparis, D; Papasiopi, N; Xenidis, A; Dermatas, D; Chrysochoou, M

2015-03-01

286

Characteristics and Mobility of Zero-Valent Nano-Iron in Porous Media  

E-print Network

of Earth Sciences Environmental Hydrogeology Group Supervisor: Dr. Ruud Schotting, schotting@geo.9.1 Transport in a Horizontal Capillary Tube . . . . . . . . . . . . . . . . . . . . . 27 #12;Contents iii 2

Cirpka, Olaf Arie

287

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

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

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

2004-01-01

288

Biogeochemistry of two types of permeable reactive barriers, organic carbon and iron-bearing organic carbon for mine drainage treatment: column experiments.  

PubMed

Permeable reactive barriers (PRBs) are an alternative technology to treat mine drainage containing sulfate and heavy metals. Two column experiments were conducted to assess the suitability of an organic carbon (OC) based reactive mixture and an Fe(0)-bearing organic carbon (FeOC) based reactive mixture, under controlled groundwater flow conditions. The organic carbon mixture contains about 30% (volume) organic carbon (composted leaf mulch) and 70% (volume) sand and gravel. The Fe(0)-bearing organic carbon mixture contains 10% (volume) zero-valent iron, 20% (volume) organic carbon, 10% (volume) limestone, and 60% (volume) sand and gravel. Simulated groundwater containing 380 ppm sulfate, 5 ppm As, and 0.5 ppm Sb was passed through the columns at flow rates of 64 (the OC column) and 62 (the FeOC column) ml d(-1), which are equivalent to 0.79 (the OC column) and 0.78 (the FeOC column) pore volumes (PVs) per week or 0.046 m d(-1) for both columns. The OC column showed an initial sulfate reduction rate of 0.4 micromol g (OC)(-1) d(-1) and exhausted its capacity to promote sulfate reduction after 30 PVs, or 9 months of flow. The FeOC column sustained a relatively constant sulfate reduction rate of 0.9 micromol g (OC)(-1) d(-1) for at least 65 PVs (17 months). In the FeOC column, the delta34S values increase with the decreasing sulfate concentration. The delta34S fractionation follows a Rayleigh fractionation model with an enrichment factor of 21.6 per thousand. The performance decline of the OC column was caused by the depletion of substrate or electron donor. The cathodic production of H2 by anaerobic corrosion of Fe probably sustained a higher level of SRB activity in the FeOC column. These results suggest that zero-valent iron can be used to provide an electron donor in sulfate reducing PRBs. A sharp increase in the delta(13)C value of the dissolved inorganic carbon and a decrease in the concentration of HCO3- indicate that hydrogenotrophic methanogenesis is occurring in the first 15 cm of the FeOC column. PMID:19467564

Guo, Qiang; Blowes, David W

2009-07-21

289

Biogeochemistry of two types of permeable reactive barriers, organic carbon and iron-bearing organic carbon for mine drainage treatment: Column experiments  

NASA Astrophysics Data System (ADS)

Permeable reactive barriers (PRBs) are an alternative technology to treat mine drainage containing sulfate and heavy metals. Two column experiments were conducted to assess the suitability of an organic carbon (OC) based reactive mixture and an Fe 0-bearing organic carbon (FeOC) based reactive mixture, under controlled groundwater flow conditions. The organic carbon mixture contains about 30% (volume) organic carbon (composted leaf mulch) and 70% (volume) sand and gravel. The Fe 0-bearing organic carbon mixture contains 10% (volume) zero-valent iron, 20% (volume) organic carbon, 10% (volume) limestone, and 60% (volume) sand and gravel. Simulated groundwater containing 380 ppm sulfate, 5 ppm As, and 0.5 ppm Sb was passed through the columns at flow rates of 64 (the OC column) and 62 (the FeOC column) ml d - 1 , which are equivalent to 0.79 (the OC column) and 0.78 (the FeOC column) pore volumes (PVs) per week or 0.046 m d - 1 for both columns. The OC column showed an initial sulfate reduction rate of 0.4 µmol g (OC) - 1 d - 1 and exhausted its capacity to promote sulfate reduction after 30 PVs, or 9 months of flow. The FeOC column sustained a relatively constant sulfate reduction rate of 0.9 µmol g (OC) - 1 d - 1 for at least 65 PVs (17 months). In the FeOC column, the ?34S values increase with the decreasing sulfate concentration. The ?34S fractionation follows a Rayleigh fractionation model with an enrichment factor of 21.6‰. The performance decline of the OC column was caused by the depletion of substrate or electron donor. The cathodic production of H 2 by anaerobic corrosion of Fe probably sustained a higher level of SRB activity in the FeOC column. These results suggest that zero-valent iron can be used to provide an electron donor in sulfate reducing PRBs. A sharp increase in the ?13C value of the dissolved inorganic carbon and a decrease in the concentration of HCO 3- indicate that hydrogenotrophic methanogenesis is occurring in the first 15 cm of the FeOC column.

Guo, Qiang; Blowes, David W.

2009-07-01

290

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...

291

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

PubMed

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 50mg/L NO3-N within 60min. 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

Ileri, Burcu; Ayyildiz, Onder; Apaydin, Omer

2015-07-15

292

THE EFFECT OF SMECTITE ON THE CORROSION OF IRON METAL  

SciTech Connect

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.

Balko, Barbara A.; Bosse, Stephanie A.; Cade, Anne E.; Jones-Landry, Elise F.; Amonette, James E.; Daschbach, John L.

2012-04-24

293

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...

294

Iron supplementation: overcoming technical and practical barriers.  

PubMed

Iron supplementation is probably the best available option to effectively address iron deficiency in pregnant women and young children because it can be targeted specifically to these high-risk groups. However, technical and practical barriers exist: limited information on the effectiveness of supplementation interventions, side effects that affect compliance, and supply/distribution constraints. An innovative approach to addressing these constraints is the use of sprinkles of powdered, microencapsulated ferrous fumarate that can be added directly to any semi-liquid food without changing their taste or consistency. This technique has been tested in initial trials in Ghana and found to be as effective as iron drops. Another approach to improve the effectiveness of iron interventions is through information, education and communication (IEC) programs. These interventions can help modify consumer behavior in some cases, but in some countries, geographic location, variations in language and population size can make the cost of IEC programs very high. IEC strategies in Indonesia aimed at increasing demand for iron supplements by systematic dissemination of specific messages, improving the quality and variety of tablets, increasing the availability and access to supplements by engaging the commercial sector, enrolling traditional birth attendants and other community volunteers in selling supplements. Key issues to be addressed include clarifying optimal starting points and duration of supplementation interventions--based on individual status or population prevalence, defining hemoglobin and ferritin cutoffs at which treatment should be instigated and evaluating the effectiveness of intermittent supplementation with multiple micronutrients. PMID:11925496

Mora, Jose O

2002-04-01

295

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

PubMed

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

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

2014-01-30

296

Groundwater Performance Monitoring of an Iron Permeable Reactive Barrier  

Microsoft Academic Search

Azimuth controlled vertical hydraulic fracturing technology constructed a full scale in situ iron permeable reactive barrier (PRB) at moderate depth at a Superfund site for remediation of groundwater contaminated with chlorinated solvents, primarily trichloroethene (TCE). The iron permeable reactive barrier was completed in late 1999 and was two hundred and forty (240) feet in length, three (3) inches in average

Grant Hocking; Samuel L. Wells

297

Biogeochemical mineralogical, and hydrological characteristics of an iron reactive barrier used for treatment of uranium and other contaminants  

SciTech Connect

A permeable iron reactive barrier was installed in late November, 1997 at the U.S. Department of Energy's Y-12 National Security Complex in Oak Ridge, Tennessee. The overall goal of this research was to determine the effectiveness of the use of zero-valent iron (Fe{sup 0}) to retain or remove uranium and other contaminants such as technetium and nitrate in groundwater. The long-term performance issues were investigated by studying the biogeochemical interactions between Fe{sup 0} and groundwater constituents and the mineralogical and biological characteristics over an extended field operation. Results from nearly 3 years of monitoring indicated that the Fe{sup 0} barrier was performing effectively in removing contaminant radionuclides such as uranium and technetium. In addition, a number of groundwater constituents such as bicarbonates, nitrate, and sulfate were found to react with the Fe{sup 0}. Both nitrate and sulfate were reduced within or in the influence zone of the Fe{sup 0} with a low redox potential (i.e., low Eh). An increased anaerobic microbial population was also observed within and in the vicinity of the Fe{sup 0} barrier, and these microorganisms were at least partially responsible for the reduction of nitrate and sulfate in groundwater. Decreased concentrations of Ca{sup 2+} and bicarbonate in groundwater occurred as a result of the formation of minerals such as aragonite (CaCO{sub 3}) and siderite (FeCO{sub 3}), which coincided with the Fe{sup 0} corrosion and an increased groundwater pH. A suite of mineral precipitates was identified in the Fe{sup 0} barrier system, including amorphous iron oxyhydroxides, goethite, ferrous carbonates and sulfides, aragonite, and green rusts. These minerals were found to be responsible for the cementation and possibly clogging of Fe{sup 0} filings observed in a number of core samples from the barrier. Significant increases in cementation of the Fe{sup 0} occurred between two coring events conducted at {approx}1 year apart and appeared to correspond to the changes in an apparent decrease in hydraulic gradient and connectivity. The present study concludes that, while Fe{sup 0} may be used as an effective reactive medium for the retention or degradation of many redox-sensitive contaminants, its long-term reactivity and performance could be severely hindered by its reactions with other groundwater constituents; and groundwater flow may be restricted because of the build up of mineral precipitates at the soil/Fe{sup 0} interface. Depending on the site biogeochemical conditions, the rate of Fe{sup 0} corrosion may increase; therefore, the life span of the Fe{sup 0} barrier could be shorter than predicted in previous studies ({approx}15-30 years).

Gu, Baohua [ORNL; Watson, David B [ORNL; Phillips, Debra H. [Queen's University, Belfast; Liang, Liyuan [ORNL

2002-05-01

298

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

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.

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

2005-12-14

299

Chemistry and microbiology of permeable reactive barriers for in situ groundwater clean up.  

PubMed

Permeable reactive barriers (PRBs) are receiving a great deal of attention as an innovative, cost-effective technology for in situ clean up of groundwater contamination. A wide variety of materials are being proposed for use in PRBs, including zero-valent metals (e.g., iron metal), humic materials, oxides, surfactant-modified zeolites (SMZs), and oxygen- and nitrate-releasing compounds. PRB materials remove dissolved groundwater contaminants by immobilization within the barrier or transformation to less harmful products. The primary removal processes include: (1) sorption and precipitation, (2) chemical reaction, and (3) biologically mediated reactions. This article presents an overview of the mechanisms and factors controlling these individual processes and discusses the implications for the feasibility and long-term effectiveness of PRB technologies. PMID:11192023

Scherer, M M; Richter, S; Valentine, R L; Alvarez, P J

2000-01-01

300

Removal of Nitrate and Ammonium ions from Livestock Wastewater by Hybrid Systems Composed of Zero-Valent Iron and Adsorbents  

Microsoft Academic Search

The feasibility of hybrid systems for simultaneous removal of nitrate (NO) and ammonium ions (NH) from livestock wastewater was examined in batch experiments. As a part of efforts to remove nitrate and ammonium simultaneously, Fe and adsorbents including coconut-based granular activated carbon (GAC), sepiolite and filtralite were used. Various parameters such as adsorbent dosages and temperature were studied. Removal of

Min-Kyu Ji; Yong-Tae Ahn; Moonis Ali Khan; Reda A. I. Abou-Shanab; Yunchul Cho; Jae-Young Choi; Yong Je Kim; Hocheol Song; Byong-Hun Jeon

2011-01-01

301

A MD Simulation and Analysis for Aggregation Behaviors of Nanoscale Zero-Valent Iron Particles in Water via MS  

PubMed Central

With the development of nanotechnology, more nanomaterials will enter into water environment system. Studying the existing form of nanomaterials in water environment will help people benefit from the correct use of them and to reduce the harm to human caused by them for some nanomaterials can bring polluting effect. Aggregation is a main behavior for nanoparticle in water environment. NZVI are used widely in many fields resulting in more NZVI in water environment. Molecular dynamics simulations and Materials Studio software are used to investigate the microaggregation behaviors of NZVI particles. Two scenes are involved: (1) particle size of NZVI in each simulation system is the same, but initial distance of two NZVI particles is different; (2) initial distance of two NZVI particles in each simulation system is the same, but particle size of NZVI is different. Atomistic trajectory, NP activity, total energy, and adsorption of H2O are analyzed with MS. The method provides new quantitative insight into the structure, energy, and dynamics of the aggregation behaviors of NZVI particles in water. It is necessary to understand microchange of NPs in water because it can provide theoretical research that is used to reduce polluting effect of NPs on water environment. PMID:25250388

Liu, Dongmei; Tang, Huan; Lu, Jing; Cui, Fuyi

2014-01-01

302

Conversion of Steel Mill's Surface Waste into Zero Valent Iron (ZVI) Nanoparticles for Hydrogen Generation for PEMFCs  

E-print Network

, photocatalysis and high temperature electrocatalysis of water and, sulfur-iodine cycle in a nuclear reactor by CO/CO2 emission. Recently, a novel, solution-based room temperature technique using an aqueous

Azad, Abdul-Majeed

303

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

USGS Publications Warehouse

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.

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

2001-01-01

304

Low frequency electrical properties of corroded iron barrier cores.  

PubMed

We investigated the electrical signatures of iron corrosion and mineral precipitation in angle cores from an Fe(0) barrier installation in operation for eight years. The real and imaginary parts of the complex electrical conductivity measured between 0.1 and 1000 Hz were 2-10 times higher (varying between cores) in the reacted zone at the upgradient edge of the barrier relative to less altered locations inside the barrier. Scanning electron microscopy identified iron surface alteration with the thickest corrosion rinds closest to the upgradient soil/iron interface. Surface area of iron minerals was also greatest at the upgradient interface, gradually decreasing into the cores. X-ray diffractometry identified precipitation of iron oxide/hydroxide, carbonate minerals, iron sulfide, as well as green rusts, with mineral complexity decreasing away from the interface. The electrical measurements correlate very well with the solid-phase analyses, and they verify that electrical methods could be used to assess or monitor iron corrosion and mineral precipitation occurring in Fe(0) barriers. PMID:16646461

Wu, Yuxin; Slater, Lee D; Korte, Nic

2006-04-01

305

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

PubMed

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

Dong, Guohui; Ai, Zhihui; Zhang, Lizhi

2014-12-01

306

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...

307

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

NASA Astrophysics Data System (ADS)

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.

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

2011-11-01

308

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

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

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

2011-11-01

309

Iron Barrier Walls for Chlorinated Solvent Remediation  

Microsoft Academic Search

\\u000a Over the past decade, permeable reactive barrier (PRB) technology has progressed through the conceptual, experimental and\\u000a innovative stages to its current status as accepted standard practice for groundwater remediation. As represented in the schematic\\u000a of Figure 16.1, a PRB can be defined as an in situ treatment zone positioned such that it passively captures a contaminant plume and removes or

Robert W. Gillham; John Vogan; Lai Gui; Michael Duchene; Jennifer Son

310

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

SciTech Connect

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.

Robert S. Bowman; Pengfei Zhang; Xian Tao

2002-03-01

311

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

Microsoft Academic Search

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

Tony R. Lee; Richard T. Wilkin

2010-01-01

312

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,...

313

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, ...

314

Monitoring Performance of a Dual Wall Permeable Reactive Barrier for Treating Perchlorate and TCE  

Microsoft Academic Search

AMEC Geomatrix, through collaboration with Aerojet General Corporation and the University of California, Davis (UCD), has performed work leading to the installation of a dual wall permeable reactive barrier (PRB) system capable of treating perchlorate and chlorinated aliphatic hydrocarbon compounds (CAHs), including trichloroethylene (TCE), at Aerojet's Area 40 site in Sacramento, California. This unique system consisted of an upgradient zero-valent

C. E. Dowman; Y. Hashimoto; S. Warner; P. Bennett; D. Gandhi; F. Szerdy; S. Neville; C. Fennessy; K. M. Scow

2008-01-01

315

Immobilization of Se(VI) in mine drainage by permeable reactive barriers: column performance  

Microsoft Academic Search

The potential for immobilization of Se in mine drainage water using a permeable reactive barrier was investigated by a column study, in which the reactive components were zero valent Fe, municipal leaf compost, sawdust, and wood chips. These components were mixed with silica sand and gravel. Trace amounts of creek sediment were added to serve as a source of anaerobic

K. Sasaki; D. W. Blowes; C. J. Ptacek; W. D. Gould

2008-01-01

316

Accumulation Rate of Microbial Biomass at Two Permeable Reactive Barrier Sites  

NASA Astrophysics Data System (ADS)

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 and permeability. Results are presented from solid phase and groundwater monitoring studies conducted at two Permeable Reactive Barrier sites, U.S. Coast Guard Support Center (Elizabeth City, North Carolina) and the Denver Federal Center (Lakewood, Colorado). At both sites barrier installations have been in place for approximately five years. Over this period, consistent patterns of spatially heterogeneous microbial biomass accumulation are observed at these sites. The iron-aquifer interface witnesses the greatest accumulation of microbial biomass and mineral precipitates. There accumulation rates are a factor of 3 to 10 times greater than midwall or downgradient regions. Estimates of porosity loss due to mineral and biomass buildup range from about 1 to 5 percent per year of the initial available volume. Phospholipid fatty acid profiles indicate that the PRB biomass is dominated by biomarkers indicative of anaerobic sulfate reducing or iron reducing bacteria. This result is in agreement with acid volatile sulfide concentrations that strongly correlate with biomass concentrations. Upgradient groundwater chemistry and flow rate appear to be the main factors that control the rate (and type) of mineral precipitate formation as well as the rate of biomass accumulation. Notice, this is an abstract of a proposed presentation and does not necessarily reflect EPA policy.

Wilkin, R.; Sewell, G.; Puls, R.

2001-12-01

317

I. Hole-transporting dendrimers and their use in organic light-emitting devices (OLEDs) and II. Novel layered catalysts containing bipyridinium and zero-valent metal species  

NASA Astrophysics Data System (ADS)

A series of polyaromatic ether/ester dendrimers containing a hole transporting naphthylphenylbenzyl amine at the periphery and a variety of fluorescent dyes at the core has been studied in an effort to observe energy transfer in these species. The dyes incorporated in these dendrimers include 1,4-dihydroxyanthraquinone (quinizarin), Coumarin 343, and a benzopentathiophene. These dendrimers have been incorporated into both single layer and heterostructure organic light emitting devices (OLEDs). In the case of first generation dendrimer OLEDs, excimer/exciplex formation was predominant. In third generation dendrimers, complete energy transfer from the periphery to the dye at the core was observed both in photoluminescence spectra and electroluminescence in OLEDs. Dendrimers containing different dye cores can be combined to achieve color mixing/tuning. In addition, layered catalysts were prepared via both covalent and electrostatic means to achieve the catalytic production of hydrogen peroxide from hydrogen and oxygen. Covalent catalysts were prepared by first growing layers of zirconium and a bipyridinium containing bisphosphonate onto silica particles. Palladium and/or platinum was ion-exchanged into the structure and reduced to the zero valent metal by hydrogen gas. A second set of catalysts was prepared by electrostatically depositing polycations/polyanions onto carboxylate or amine functionalized polystyrene microspheres. Anionic colloidal particles were adsorbed to the polycationic surface. An octacationic viologen oligomer was used in an attempt to increase the affinity of adsorption of the Pd particles to the surface of the microspheres. Catalytic studies of both types of catalysts are herein reported.

Koene, Shannon Carol

318

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 zero?valent 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...

319

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

USGS Publications Warehouse

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.

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

2009-01-01

320

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...

321

Reductive denitrification of nitrate by scrap iron filings*  

PubMed Central

Reduction of nitrate by zero-valent iron is a highly exergonic reaction that has long been known to occur. Use of scrap iron filings (SIF) as the PRB (Permeable Reactive Barrier) material can be used to recycle certain by-products, and identify cheaper replacements for expensive conventional PRB materials, especially pure metallic iron. The feasibility of reductive denitrification of nitrate by SIF was studied by batch experiments. Operational parameters such as pH value, SIF dosage and initial concentration of nitrate were investigated. The removal efficiency of nitrate reached 80% under the conditions of pH of 2.5, nitrate initial concentration of 45 mg/L and SIF dosage of 100 g/L within 4 h. Results indicated that nitrate removal is inversely related to pH. Low pH value condition favors for the nitrate transformation. Different from the results of others who studied nitrate reduction using iron powder, we found that there was a lag time before nitrate reduction occurs, even at low pH. Finally, the possible mechanism of nitrate reduction by Fe0 is discussed. PMID:15682502

Hao, Zhi-wei; Xu, Xin-hua; Wang, Da-hui

2005-01-01

322

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

NASA Astrophysics Data System (ADS)

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.

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

2013-08-01

323

Intrinsic Barriers for Electron and Hydrogen Atom Transfer Reactions of Biomimetic Iron Complexes  

E-print Network

Intrinsic Barriers for Electron and Hydrogen Atom Transfer Reactions of Biomimetic Iron Complexes) Meunier, B., Ed. Biomimetic Oxidations Catalyzed by Transition Metal Complexes; Imperial College Press

Roth, Justine P.

324

APPLICATIONS OF SURFACE ANALYSIS IN THE ENVIRONMENTAL SCIENCES: DEHALOGENATION OF CHLOROCARBONS WITH ZERO-VALENT IRON AND IRON-CONTAINING MINERAL SURFACES. (R828771C006)  

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...

325

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...

326

A new method to produce nanoscale iron for nitrate removal  

Microsoft Academic Search

This article proposes a novel technology combining electrochemical and ultrasonic methods to produce nanoscale zero valent iron (NZVI). With platinum placed in the cathode and the presence of the dispersion agent, 0.2g\\/l cetylpyridinium chloride (CPC), a cation surfactant, in the solution, the nanoscale iron particle was successfully produced with diameter of 1–20 nm and specific surface area of 25.4m2\\/g. The

Shiao-Shing Chen; Hong-Der Hsu; Chi-Wang Li

2004-01-01

327

Phosphate Barriers for Immobilization of Uranium Plumes  

SciTech Connect

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.

Burns, Peter C.

2004-12-01

328

Phosphate Barriers for Immobilization of Uranium Plumes  

SciTech Connect

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.

Icenhower, Jonathan P.; Burns, Peter C.

2005-06-01

329

Performance of a Deep Iron Permeable Reactive Barrier for Groundwater Remediation of VOCs  

Microsoft Academic Search

Azimuth controlled vertical hydraulic fracturing technology constructed a full scale in situ iron permeable reactive barrier (PRB) at moderate depth at a Superfund site in south eastern Iowa for remediation of groundwater contaminated with chlorinated solvents, primarily trichlorooethene (TCE). The iron permeable reactive barrier was completed in late 1999 and was two hundred and forty (240) feet in length, three

Grant Hocking; Samuel L. Wells; Rafael I. Ospina; Golder Sierra; LLC Atlanta

330

Reactive transport modeling of an in situ reactive barrier for the treatment of hexavalent chromium and trichloroethylene in groundwater  

NASA Astrophysics Data System (ADS)

Multicomponent reactive transport modeling was conducted for the permeable reactive barrier at the Coast Guard Support Center near Elizabeth City, North Carolina. The zero-valent iron barrier was installed to treat groundwater contaminated by hexavalent chromium and chlorinated solvents. The simulations were performed using the reactive transport model MIN3P, applied to an existing site-specific conceptual model. Reaction processes controlling the geochemical evolution within and down gradient of the barrier were considered. Within the barrier, the treatment of the contaminants, the reduction of other electron acceptors present in the ambient groundwater, microbially mediated sulfate reduction, the precipitation of secondary minerals, and degassing of hydrogen gas were included. Down gradient of the barrier, water-rock interactions between the highly alkaline and reducing pore water emanating from the barrier and the aquifer material were considered. The model results illustrate removal of Cr(VI) and the chlorinated solvents by the reactive barrier and highlight that reactions other than the remediation reactions most significantly affect the water chemistry in the barrier. In particular, sulfate reduction and iron corrosion by water control the evolution of the pore water while passing through the treatment system. The simulation results indicate that secondary mineral formation has the potential to decrease the porosity in the barrier over the long term and illustrate that the precipitation of minerals is concentrated in the upgradient portion of the barrier. Two-dimensional simulations demonstrate how preferential flow can affect the reduction of electron acceptors, the consumption of the treatment material, and the formation of secondary minerals. In addition, the model results indicate that deprotonation and the adsorption of cations down gradient of the barrier can potentially explain the observed pH buffering.

Mayer, K. Ulrich; Blowes, David W.; Frind, Emil O.

2001-12-01

331

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

NASA Astrophysics Data System (ADS)

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.

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

2006-12-01

332

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

SciTech Connect

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.

Wilkin, Richard T.; Lee, T.R. (U.S. EPA)

2010-10-22

333

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

NASA Astrophysics Data System (ADS)

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 (? fG°) 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.

Lee, Tony R.; Wilkin, Richard T.

2010-07-01

334

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...

335

Treatment of inorganic contaminants using permeable reactive barriers  

NASA Astrophysics Data System (ADS)

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.

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

2000-09-01

336

Geomicrobiological Regeneration of Iron Sulfides in Engineered barrier Systems  

NASA Astrophysics Data System (ADS)

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.

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

2005-12-01

337

Evaluation of barrier materials for removing pollutants from groundwater rich in natural organic matter.  

PubMed

Permeable barriers are used for passive remediation of groundwater and can be constructed from a range of materials. The optimal material depends on the types of contaminants and physico-chemical parameters present at the site, as well as the hydraulic conductivity, environmental safety, availability, cost and long-term stability of the material itself. The aim of the presented study was to test a number of materials for their ability to remove heavy metals and organic pollutants from groundwater with a high (140 mg L(-1)) content of natural organic matter (NOM). The following materials were included in the study: sand, peat, fly ash, iron powder, lignin and combinations thereof. Polluted water was fed into glass columns loaded with each sorbent and the contaminant removal efficiency of the material was evaluated through chemical analysis of the percolate. Materials based on fly ash and zero-valent iron were found to be the most effective for heavy metal removal, while fly ash and peat were the most effective for removing aliphatic compounds. Filtration through lignin and peat led to leaching of NOM. Although the leaching decreased over time, it remained high throughout the experiments. The results indicate that remediation of contaminated land at disused industrial sites is a complex task that often requires the use of mixed materials or a minimum of two sequential barriers. PMID:25026576

Kozyatnyk, I; Haglund, P; Lövgren, L; Tysklind, M; Gustafsson, A; Törneman, N

2014-01-01

338

Electrical Properties of Reacted Iron Cores Extracted From a Permeable Reactive Barrier Installation  

NASA Astrophysics Data System (ADS)

We conducted experiments to investigate the application of non-invasive electrical method for monitoring iron corrosion and mineral precipitation processes on angle cores recovered from the Kansas City Plant reactive iron barrier. Electrical measurements showed continuous changes from the soil/iron interface into the barrier for all three cores. Scanning electron microscopy (SEM) identified iron surface alteration with thickest corrosion rind, indicating most severe corrosion, occurred close to upgradient soil/iron interface relative to locations further into the cores. Nitrogen adsorption measurements showed decreases in specific surface area of iron minerals from upgradient soil/iron interface into the barrier. X-ray diffractometry (XRD) identified precipitation of iron oxide/hydroxide, carbonate minerals, iron sulfide as well as green rusts in all three cores, and magnetite was identified as the dominant phase. Electrical measurements correlated well with solid phase analysis and illustrated the sensitivity of low frequency electrical method to iron corrosion and mineral precipitation processes. Electrical signature changes are attributed to (1) higher complex interfacial conductivity due to increased surface area and mineralogical alteration, and (2) increased electronic conduction due to enhanced electron transfer across the iron-fluid interface facilitated by mineralogical alternation and increased specific surface area during iron corrosion and mineral precipitation. Electrical measurements along with solid phase analysis also revealed more severe corrosion occurred at north end relative to south end of the barrier correlated with more groundwater flow through north end of the barrier. Our results on field cores are consistent with laboratory studies on synthetic iron columns presented previously and demonstrate that electrical measurements are a proxy indicator of Fe0 surface alteration and could be implemented for field barrier corrosion process monitoring.

Wu, Y.; Slater, L.; Korte, N.

2005-12-01

339

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) ...

340

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

PubMed

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 3.7 E-1 m d(-1). Dissolved contaminants (PCE, TCE, cis-DCE, trans-DCE and VC) and inorganic (Ca(2+), Fe(2+), 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 1.4 E-3m 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. PMID:23174212

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

2012-11-01

341

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

NASA Astrophysics Data System (ADS)

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.

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

2012-11-01

342

Coupled acidification and ultrasound with iron enhances nitrate reduction  

Microsoft Academic Search

Contaminated soils, especially when pollutant concentrations are high, pose potentially serious threats to surface and groundwater quality, when there are spills, discharges, or leaking storage tanks. For in situ remediation of nitrate in groundwater, the use of zero-valent iron (Fe0) is suggested. The formation of passivating scales on Fe0 over time may limit the long-term reduction potential of Fe0. The

Yih-Jin Tsai; Feng-Chih Chou; Tsung-Chieh Cheng

2009-01-01

343

Effects of Mineral Precipitation on the Long-term Performance of Granular Iron Permeable Reactive Barriers  

Microsoft Academic Search

Granular iron permeable reactive barriers (PRBs) have received considerable attention as long term, low-maintenance remediation solutions for groundwater contaminated with chlorinated organics, heavy metals, and radionuclides. However, the long-term effects of mineral precipitation on the performance of the iron still remain uncertain. Laboratory column experiments and numerical simulations were conducted to evaluate the effects of mineral precipitation on the permeability

S. Jeen; D. W. Blowes; R. W. Gillham

2004-01-01

344

Effects of initial iron corrosion rate on long-term performance of iron permeable reactive barriers: Column experiments and numerical simulation  

Microsoft Academic Search

Column experiments and numerical simulation were conducted to test the hypothesis that iron material having a high corrosion rate is not beneficial for the long-term performance of iron permeable reactive barriers (PRBs) because of faster passivation of iron and greater porosity loss close to the influent face of the PRBs. Four iron materials (Connelly, Gotthart-Maier, Peerless, and ISPAT) were used

Jin suk O; Sung-Wook Jeen; Robert W. Gillham; Lai Gui

2009-01-01

345

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

Microsoft Academic Search

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

2003-01-01

346

Ferritin polarization and iron transport across monolayer epithelial barriers in mammals  

PubMed Central

Epithelial barriers are found in many tissues such as the intestine, kidney and brain where they separate the external environment from the body or a specific compartment from its periphery. Due to the tight junctions that connect epithelial barrier-cells (EBCs), the transport of compounds takes place nearly exclusively across the apical or basolateral membrane, the cell-body and the opposite membrane of the polarized EBC, and is regulated on numerous levels including barrier-specific adapted trafficking-machineries. Iron is an essential element but toxic at excess. Therefore, all iron-requiring organisms tightly regulate iron concentrations on systemic and cellular levels. In contrast to most cell types that control just their own iron homeostasis, EBCs also regulate homeostasis of the compartment they enclose or the body as a whole. Iron is transported across EBCs by specialized transporters such as the transferrin receptor and ferroportin. Recently, the iron storage protein ferritin was also attributed a role in the regulation of systemic iron homeostasis and we gathered evidence from the literature and original data that ferritin is polarized in EBC, suggesting also a role for ferritin in iron trafficking across EBCs. PMID:25202274

Meyron-Holtz, Esther G.; Cohen, Lyora A.; Fahoum, Lulu; Haimovich, Yael; Lifshitz, Lena; Magid-Gold, Inbar; Stuemler, Tanja; Truman-Rosentsvit, Marianna

2014-01-01

347

Heterotrophic\\/autotrophic denitrification (HAD) of drinking water: prospective use for permeable reactive barrier  

Microsoft Academic Search

This work aims to explore the use of an innovative denitrification process developed by our group for groundwater remediation. This process is coupling heterotrophic-autotrophic denitrification processes (HAD) supported by cotton and zero-valent iron (ZVI). In the experimental part, the effect of two amounts of ZVI (150 and 300 g), two nitrate (100 and 220 mg\\/l) and phosphate (3 and 6

Claudio Della Rocca; Vincenzo Belgiorno; Sureyya Meriç

2007-01-01

348

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

Microsoft Academic Search

Pyrite formation has been investigated at 70°C and pH 6–8 by aging precipitated, disordered mackinawite, Fe9S8, and greigite, Fe3S4, in solutions containing aqueous H2S, HS?, Sx2?, S2O32?, SO32?, 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

R. T. Wilkin; H. L. Barnes

1996-01-01

349

IN-SITU REMOVAL OF ARSENIC FROM GROUNDWATERS BY USING PERMEABLE REACTIVE BARRIERS OF ORGANIC MATTER\\/LIMESTONE MIXTURES  

Microsoft Academic Search

In this study, two different mixtures of municipal compost, limestone and zero-valent iron were assessed in two column experiments on acid rock treatment. The effluent solution was systematically analysed throughout the experiments and precipitates from both columns were withdrawn for scanning electron microscopy, energy-dispersive X-ray spectroscopy and X-ray diffractometry were analyzed. Results showed that waters were cleaned of metals, arsenic

O. Gibert; J. de Pablo; J-L Cortina; C. Ayora; J. Cam

350

Chemical stabilization of metals in mine wastes by transformed red mud and other iron compounds: laboratory tests.  

PubMed

A series of static and kinetic laboratory-scale tests were designed in order to evaluate the efficacy of transformed red mud (TRM) from bauxite refining residues, commercial zero-valent iron, and synthetic iron (III) hydroxides as sorbents/reagents to minimize the generation of acid drainage and the release of toxic elements from multi-contaminant-laden mine wastes. In particular, in some column experiments the percolation of meteoric water through a waste pile, alternated with periods of dryness, was simulated. Wastes were placed in columns together with sorbents/reagents in three different set-ups: as blended amendment (mixing method), as a bed at the bottom of the column (filtration method), or as a combination of the two previous methods. The filtration methods, which simulate the creation of a permeable reactive barrier downstream of a waste pile, are the most effective, while the use of sorbents/reagents as amendments leads to unsatisfactory results, because of the selective removal of only some contaminants. The efficacy of the filtration method is not significantly affected by the periods of dryness, except for a temporary rise of metal contents in the leachates due to dissolution of soluble salts formed upon evaporation in the dry periods. These results offer original information on advantages/limits in the use of TRM for the treatment of multi-contaminant-laden mine wastes, and represent the starting point for experimentation at larger scale. PMID:25244134

Ardau, C; Lattanzi, P; Peretti, R; Zucca, A

2014-01-01

351

Phosphate Barriers for Immobilization of Uranium Plumes  

SciTech Connect

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.

Burns, Peter C.

2005-06-01

352

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...

353

Monitoring trichloroethene remediation at an iron permeable reactive barrier using stable carbon isotopic analysis  

Microsoft Academic Search

Stable carbon isotopic analysis, in combination with compositional analysis, was used to evaluate the performance of an iron permeable reactive barrier (PRB) for the remediation of ground water contaminated with trichloroethene (TCE) at Spill Site 7 (SS7), F.E. Warren Air Force Base, Wyoming. Compositional data indicated that although the PRB appeared to be reducing TCE to concentrations below treatment goals

Nancy Vanstone; Andrzej Przepiora; John Vogan; Georges Lacrampe-Couloume; Brian Powers; Ernesto Perez; Scott Mabury; Barbara Sherwood Lollar

2005-01-01

354

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...

355

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...

356

Performance evaluation of a pilot-scale permeable reactive barrier at former Naval Air Station Moffett Field, Mountain View, California: Volume 1. Final report, April 1996--November 1998  

SciTech Connect

A pilot scale permeable reactive barrier (PRB) or treatment wall demonstration project was initiated by the US Navy EFA West at the former Naval Air Station Moffett Field site in Mountain View, California about 3 years ago. Performance evaluations and cost-benefit analyses were performed by the US Naval Facilities Engineering Service Center (NFESC) and were sponsored by the Department of Defense (DoD) Environmental Security Technology Certification Program (ESTCP). The Moffett Field PRB uses a funnel-and-gate design, where the funnel is made of interlocking steel sheet piles and the gate consists of a reactive cell filled with zero-valent granular iron. Since its construction in April 1996, groundwater monitoring was conducted on a quarterly basis to demonstrate the effectiveness of the barrier technology in capturing and remediating groundwater that contained dissolved chlorinated hydrocarbon compounds. The primary contaminants of concern at Moffett Field in the vicinity of the PRB are trichloroethene, cis-1,2 dichloroethene, and perchloroethene at upgradient concentrations of about 2900 micrograms per liter, 280 micrograms/L, and 26 microgram/L, respectively. Quarterly monitoring events included water level measurements, field parameter testing, and groundwater sampling at about 75 monitoring points. Two tracer tests using bromide solutions and flow meter testing were also completed in April and August 1997 at the site. Iron cell coring samples were collected and analyzed in December 1997 for use as indicators of reactivity and longevity. Data from the quarterly monitoring, tracer testing, and iron cell coring have been used to determine the overall barrier performance. Since the first sampling event in June 1996, concentrations of all chlorinated compounds were either reduced to non-detect or to below the drinking water maximum contaminant levels within the first 2-3 feet of the permeable iron cell.

Reeter, C.; Gavaskar, A.; Sass, B.; Gupta, N.; Hicks, J.

1998-11-01

357

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

SciTech Connect

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.

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

358

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

SciTech Connect

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.

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

359

Comparison study of ferrofluid and powder iron oxide nanoparticle permeability across the blood–brain barrier  

PubMed Central

In the present study, the permeability of 11 different iron oxide nanoparticle (IONP) samples (eight fluids and three powders) was determined using an in vitro blood–brain barrier model. Importantly, the results showed that the ferrofluid formulations were statistically more permeable than the IONP powder formulations at the blood–brain barrier, suggesting a role for the presently studied in situ synthesized ferrofluid formulations using poly(vinyl) alcohol, bovine serum albumin, collagen, glutamic acid, graphene, and their combinations as materials which can cross the blood–brain barrier to deliver drugs or have other neurological therapeutic efficacy. Conversely, the results showed the least permeability across the blood–brain barrier for the IONP with collagen formulation, suggesting a role as a magnetic resonance imaging contrast agent but limiting IONP passage across the blood–brain barrier. Further analysis of the data yielded several trends of note, with little correlation between permeability and fluid zeta potential, but a larger correlation between permeability and fluid particle size (with the smaller particle sizes having larger permeability). Such results lay the foundation for simple modification of iron oxide nanoparticle formulations to either promote or inhibit passage across the blood–brain barrier, and deserve further investigation for a wide range of applications. PMID:23426527

Hoff, Dan; Sheikh, Lubna; Bhattacharya, Soumya; Nayar, Suprabha; Webster, Thomas J

2013-01-01

360

Comparison study of ferrofluid and powder iron oxide nanoparticle permeability across the blood-brain barrier.  

PubMed

In the present study, the permeability of 11 different iron oxide nanoparticle (IONP) samples (eight fluids and three powders) was determined using an in vitro blood-brain barrier model. Importantly, the results showed that the ferrofluid formulations were statistically more permeable than the IONP powder formulations at the blood-brain barrier, suggesting a role for the presently studied in situ synthesized ferrofluid formulations using poly(vinyl) alcohol, bovine serum albumin, collagen, glutamic acid, graphene, and their combinations as materials which can cross the blood-brain barrier to deliver drugs or have other neurological therapeutic efficacy. Conversely, the results showed the least permeability across the blood-brain barrier for the IONP with collagen formulation, suggesting a role as a magnetic resonance imaging contrast agent but limiting IONP passage across the blood-brain barrier. Further analysis of the data yielded several trends of note, with little correlation between permeability and fluid zeta potential, but a larger correlation between permeability and fluid particle size (with the smaller particle sizes having larger permeability). Such results lay the foundation for simple modification of iron oxide nanoparticle formulations to either promote or inhibit passage across the blood-brain barrier, and deserve further investigation for a wide range of applications. PMID:23426527

Hoff, Dan; Sheikh, Lubna; Bhattacharya, Soumya; Nayar, Suprabha; Webster, Thomas J

2013-01-01

361

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

NASA Astrophysics Data System (ADS)

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.

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

2014-11-01

362

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

PubMed

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

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

2014-11-01

363

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

PubMed Central

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

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

2015-01-01

364

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

PubMed

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

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

2015-01-01

365

Reactive Membrane Barriers for Containment of Subsurface Contamination  

SciTech Connect

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.

William A. Arnold; Edward L. Cussler

2007-02-26

366

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

Microsoft Academic Search

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

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

2008-01-01

367

Predictions of long-term performance of granular iron permeable reactive barriers: Field-scale evaluation  

Microsoft Academic Search

Long-term performance is a key consideration for the granular iron permeable reactive barrier (PRB) technology because the economic benefit relies on sustainable operation for substantial periods of time. However, predictions on the long-term performance have been limited mainly because of the lack of reliable modeling tools. This study evaluated the predictive capability of a recently-developed reactive transport model at two

Sung-Wook Jeen; Robert W. Gillham; Andrzej Przepiora

2011-01-01

368

Automated Impedance Tomography for Monitoring Permeable Reactive Barrier Health  

SciTech Connect

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.

LaBrecque, D J; Adkins, P L

2009-07-02

369

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

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.

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

1981-06-01

370

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

PubMed

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

Takahashi, Keisuke

2015-02-19

371

Numerical simulation of the interaction between granitic groundwater, engineered clay barrier and iron canister  

SciTech Connect

The geochemical evolution of a clay engineered barrier subjected simultaneously to granitic groundwater on its external boundary and to a steady flux of iron released by canister corrosion on the other boundary is simulated for time periods up to 1,000 y. A multisite ion-exchange model combined with dissolution/precipitation of accessory minerals (calcite, gypsum, quartz, geothite, pyrite, pyrrhotite, iron silicate, magnetite) is used to describe the geochemical evolution of the clay barrier. Diffusive transport of aqueous species and dissolved gases is simulated in a one dimension space. Retroaction of chemical reactions on the corrosion process of the canister is not included in the model. The temperature is assumed to be constant (25 C). Calculations are performed with the IMPACT geochemical coupled code. Two main scenarios are considered: (1) the reduction of sulfates (gypsum) is kinetically hindered, (2) the reduction of sulfates is possible and leads to the precipitation of sulfides. Main results obtained are dealing with H{sub 2}(gas) generation and control, pH transient and buffering effect of the clay barrier system. These simulations show that the hydrogen partial pressure in the clay barrier could possibly stay for long periods of time at a very low level due to interactions with mineral buffers or sinks. In the sulfate reduction scenario, a transient pH excursion is predicted at the vicinity of the canister. Future developments of this work include the taking into account of a temperature gradient. Improvement of the geochemical model and reaction pathway is also necessary and will be done with the guidance of on going experimental work.

Trotignon, L.; Faure, M.H.; Cranga, M.; Peycelon, H.

1999-07-01

372

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

SciTech Connect

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.

Wilkin, Richard T.; Su, Chunming; Ford, Robert G.; Paul, Cynthia J. (US EPA)

2008-06-09

373

RDX degradation using an integrated Fe(0)-microbial treatment approach  

E-print Network

presents proof of concept that permeable reactive iron barriers might be a viable approach to intercept. Keywords Aquifer; bioaugmentation; biodegradation; explosives; iron; Microtox; permeable reactive barriers been an explosion of activity directed at the use of zero- valent iron (Fe(0)) as a reactive material

Alvarez, Pedro J.

374

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

Microsoft Academic Search

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

David Wallace Hubble

2003-01-01

375

Reduction of selenite on iron surfaces: Amicro-spectroscopic study  

NASA Astrophysics Data System (ADS)

Under anoxie conditions zero-valent iron can react with water to produce hydrogen gas and magnetite or green rust, a highly reactive mineral phase that can induce reduction processes and thus control the speciation, the solubility, toxicity and the mobility of redox sensitive elements in (nuclear) waste repositories. In this study micro X-ray fluorescence (micro-XRF) and micro X-ray absorption spectroscopy (micro-XAS) were used to investigate the speciation of selenium that immobilized in the presence of Fe(0) and an anoxie synthetic groundwater solution. The selenium immobilization was accompanied by the formation of a green rust corrosion layer. Micro-XRF revealed that a Se-rich layer is present along the iron surfaces that were exposed to the Se(IV) solution. Micro-XAS experiments at the Se K-edge showed that Se(IV) was reduced to elemental Se(0). Thus, the reactivity of zero-valent and green rust should to be considered in assessing the long-term fate of selenium in nuclear waste repositories.

Scheidegger, A. M.; Grolimund, D.; Cui, D.; Devoy, J.; Spahiu, K.; Wersin, P.; Bonhoure, I.; Janousch, M.

2003-03-01

376

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

PubMed

Design and operation of Fe0 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 Fe0 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 Fe0 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 Fe0 section of the PRB) may last less than five more years, thus reducing the effectiveness of the PRB to mitigate contaminants. PMID:14674525

Phillips, D H; Watson, D B; Roh, Y; Gu, B

2003-01-01

377

Predictions of long-term performance of granular iron permeable reactive barriers: field-scale evaluation.  

PubMed

Long-term performance is a key consideration for the granular iron permeable reactive barrier (PRB) technology because the economic benefit relies on sustainable operation for substantial periods of time. However, predictions on the long-term performance have been limited mainly because of the lack of reliable modeling tools. This study evaluated the predictive capability of a recently-developed reactive transport model at two field-scale PRBs, both having relatively high concentrations of dissolved carbonate in the native groundwater. The first site, with 8 years of available monitoring data, was a funnel-and-gate installation, with a low groundwater velocity through the gate (about 0.12 m d(-1)). The loss in iron reactivity caused by secondary mineral precipitation was small, maintaining relatively high removal rates for chlorinated organics. The simulated concentrations for most constituents in the groundwater were within the range of the monitoring data. The second site, with monitoring data available for 5 years, was a continuous wall PRB, designed for a groundwater velocity of 0.9 m d(-1). A comparison of measured and simulated aqueous concentrations suggested that the average groundwater velocity through the PRB could be lower than the design value by a factor of two or more. The distribution and amounts of carbonate minerals measured in core samples supported the decreased groundwater velocity used in the simulation. The generally good agreement between the simulated and measured aqueous and solid-phase data suggest that the model could be an effective tool for predicting long-term performance of granular iron PRBs, particularly in groundwater with high concentrations of carbonate. PMID:21237528

Jeen, Sung-Wook; Gillham, Robert W; Przepiora, Andrzej

2011-04-01

378

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

PubMed Central

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

Luo, Jing; Farrell, James

2013-01-01

379

Environmental application of millimetre-scale sponge iron (s-Fe?) particles (I): pretreatment of cationic triphenylmethane dyes.  

PubMed

To investigate the removal capability of millimetric zero valent iron (mmZVI), sponge iron (s-Fe(0)) particles were characterized with XRD, XPS, TEM, HRSEM and EDS techniques. Moreover, the roles of particle size, catalyst dosage, dye concentration, mixing conditions (e.g. ultrasound (US), stirring or shaking), and regeneration treatment were studied with the removal of cationic triphenylmethane dyes. Notably, the reduction process was also revealed as compared to nanoscale zero valent iron (nZVI), microscale iron power, and iron scurf. Furthermore, the reductive mechanism was exemplified with brilliant green. The results demonstrated that (1) the synergetic effect between US and s-Fe(0) greatly enhanced the removal of dyes, (2) the dosage of preferred s-Fe(0) (1-3mm) particles was optimized as 30.0g/L; (3) reuse cycles of s-Fe(0) catalyst were enhanced with the assistance of diluted HCl solution; (4) the main degradation routes included the cleavage of conjugated structure reactions, N-de-ethylation reactions, hydroxylation reactions, the removal of benzene ring reactions, and opening ring reactions. Accordingly, the pretreatment of aqueous solution over s-Fe(0) was hypothesized to achieve mainly through direct reduction reaction by electron transfer and indirect reductive reactions by the highly activated hydrogen atom. Additionally, decoration with noble metals was utilized to reveal the reaction mechanism. PMID:25464285

Ju, Yongming; Liu, Xiaowen; Li, Zhaoyong; Kang, Juan; Wang, Xiaoyan; Zhang, Yukui; Fang, Jiande; Dionysiou, Dionysios D

2015-02-11

380

Review of iron-free Fenton-like systems for activating H2O2 in advanced oxidation processes.  

PubMed

Iron-catalyzed hydrogen peroxide decomposition for in situ generation of hydroxyl radicals (HO(•)) has been extensively developed as advanced oxidation processes (AOPs) for environmental applications. A variety of catalytic iron species constituting metal salts (in Fe(2+) or Fe(3+) form), metal oxides (e.g., Fe2O3, Fe3O4), and zero-valent metal (Fe(0)) have been exploited for chemical (classical Fenton), photochemical (photo-Fenton) and electrochemical (electro-Fenton) degradation pathways. However, the requirement of strict acidic conditions to prevent iron precipitation still remains the bottleneck for iron-based AOPs. In this article, we present a thorough review of alternative non-iron Fenton catalysts and their reactivity towards hydrogen peroxide activation. Elements with multiple redox states (like chromium, cerium, copper, cobalt, manganese and ruthenium) all directly decompose H2O2 into HO(•) through conventional Fenton-like pathways. The in situ formation of H2O2 and decomposition into HO(•) can be also achieved using electron transfer mechanism in zero-valent aluminum/O2 system. Although these Fenton systems (except aluminum) work efficiently even at neutral pH, the H2O2 activation mechanism is very specific to the nature of the catalyst and critically depends on its composition. This review describes in detail the complex mechanisms and emphasizes on practical limitations influencing their environmental applications. PMID:24857896

Bokare, Alok D; Choi, Wonyong

2014-06-30

381

ENVIRONMENTAL ENGINEERING SCIENCE Volume 24, Number 8, 2007  

E-print Network

within and around a zero-valent iron (ZVI) permeable reactive barrier (PRB) identified several bacteria, 2007 1123 INTRODUCTION PERMEABLE REACTIVE IRON BARRIERS (PRBs) fre- quently consist of a granular zero.1089/ees.2007.0016 Microbial Characterization of Groundwater Undergoing Treatment with a Permeable Reactive

Alvarez, Pedro J.

382

Key factors and barriers to the adoption of cold ironing in europe  

Microsoft Academic Search

The first cases of successful implementation of cold ironing can be found in Alaska about twenty years ago. In that case, the energy cost was lower than in Europe where cold ironing has been developed only in the latest years at few ports. The present paper investigates the innovative process of cold ironing at European level. Firstly, its recent development

Giulia Arduino; David G. Carrillo Murillo; David G. Claudio Ferrari

2011-01-01

383

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

SciTech Connect

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.

Wang Qiang [Department of Occupational and Environmental Health, Faculty of Military Preventive Medicine, Fourth Military Medical University, 17 Changlexi Street, Xi'an, 710032 (China); Luo Wenjing [Department of Occupational and Environmental Health, Faculty of Military Preventive Medicine, Fourth Military Medical University, 17 Changlexi Street, Xi'an, 710032 (China); Zheng Wei [School of Health Sciences, Purdue University, West Lafayette, IN (United States); Liu Yiping [Institute of Microbiology Epidemiology, Academy of Military Medical Siences, Beijing 100071 (China); Xu Hui [Department of Occupational and Environmental Health, Faculty of Military Preventive Medicine, Fourth Military Medical University, 17 Changlexi Street, Xi'an, 710032 (China); Zheng Gang [Department of Occupational and Environmental Health, Faculty of Military Preventive Medicine, Fourth Military Medical University, 17 Changlexi Street, Xi'an, 710032 (China); Dai Zhongming [Department of Occupational and Environmental Health, Faculty of Military Preventive Medicine, Fourth Military Medical University, 17 Changlexi Street, Xi'an, 710032 (China); Zhang Wenbin [Department of Occupational and Environmental Health, Faculty of Military Preventive Medicine, Fourth Military Medical University, 17 Changlexi Street, Xi'an, 710032 (China); Chen Yaoming [Department of Occupational and Environmental Health, Faculty of Military Preventive Medicine, Fourth Military Medical University, 17 Changlexi Street, Xi'an, 710032 (China); Chen Jingyuan [Department of Occupational and Environmental Health, Faculty of Military Preventive Medicine, Fourth Military Medical University, 17 Changlexi Street, Xi'an, 710032 (China)]. E-mail: jy_chen@fmmu.edu.cn

2007-02-15

384

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)

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.)

Hubble, David Wallace

385

Enrichment and encapsulation of uranium with iron nanoparticle.  

PubMed

The ability to recover uranium from water is significant because of its potential applications on nuclear fuel capture and mitigation of nuclear wastes. In this work, a unique nanostructure is presented by which trace level (2.32-882.68 ?g/L) uranium can be quickly separated from water and encapsulated at the center of zero-valent iron nanoparticles. Over 90% of the uranium is recovered with 1 g/L nanoparticles in less than 2 min. Near atomic-resolution elemental mapping on the U(VI) intraparticle reactions in a single iron nanoparticle is obtained with aberration corrected scanning transmission electron microscopy, which provides direct evidence on U(VI) diffusion, reduction to U(IV), and deposition in the core area. PMID:25689272

Ling, Lan; Zhang, Wei-Xian

2015-03-01

386

Iron  

MedlinePLUS

Iron is a mineral that our bodies need for many functions. For example, iron is part of hemoglobin, a protein which carries ... It helps our muscles store and use oxygen. Iron is also part of many other proteins and ...

387

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

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.

Siegrist, R.L. [Oak Ridge National Lab., TN (United States)] [Oak Ridge National Lab., TN (United States); [Colorado School of Mines, Golden, CO (United States). Environmental Science and Engineering Div.; Lowe, K.S. [Oak Ridge National Lab., Grand Junction, CO (United States). Life Sciences Div.] [Oak Ridge National Lab., Grand Junction, CO (United States). Life Sciences Div.; Murdoch, L.D. [FRx, Inc., Cincinnati, OH (United States)] [FRx, Inc., Cincinnati, OH (United States); [Clemson Univ., SC (United States); Slack, W.W. [FRx, Inc., Cincinnati, OH (United States)] [FRx, Inc., Cincinnati, OH (United States); Houk, T.C. [Lockheed Martin Energy Systems, Piketon, OH (United States)] [Lockheed Martin Energy Systems, Piketon, OH (United States)

1998-03-01

388

Recovery of Cr as Cr(III) from Cr(VI)-contaminated kaolinite clay by electrokinetics coupled with a permeable reactive barrier.  

PubMed

Zero-valent iron (Fe(0)) and magnetite (Fe3O4) were investigated as potential reductants in an electrokinetic/permeable reactive barrier hybrid system (EK/PRB) for the recovery of Cr as Cr(III) from Cr(VI)-contaminated kaolinite. For the EK/Fe(0) PRB, regardless of the pH in the anode well, the system facilitated the reduction of Cr(VI) into Cr(III), but the recovery of the Cr(III) in the PRB was low. Conversely, the reduction of Cr(VI) occurred only in the PRB for the EK/Fe3O4 PRB. However, when the anode pH was not controlled and the soil pH values correspondingly decreased gradually from the anode side, a greater fraction of Cr(VI) sorbed onto the kaolinite; as a result, a lower amount of Cr(VI) migrated to the Fe3O4 PRB. In addition, it was found that the majority of Cr(VI) migrating to the Fe3O4 PRB retained its oxidation state without being converted into Cr(III). These two adverse effects were mitigated by maintaining the soil pH values at 6.8, but at the same time, 18% of Cr(VI) penetrated through the Fe3O4 PRB. The penetration of Cr(VI) through the Fe3O4 PRB was successfully prevented by increasing the reaction time through the introduction of a cation exchange membrane between the Fe3O4 PRB and the anode well. PMID:24981681

Suzuki, Tasuma; Kawai, Katsunori; Moribe, Mai; Niinae, Masakazu

2014-08-15

389

Cultural and environmental barriers to adequate iron intake among northern Kenyan schoolchildren.  

PubMed

The purpose of this study was to examine the context of iron deficiency and feeding patterns of iron-rich foods among northern Kenyan school-aged children. A nutrition survey was conducted among 300 subjects in two Rendille communities, Korr and Karare. The objectives were to determine the prevalence of iron deficiency as it relates to parasitic infection, dietary intake, and sociodemographic factors, as well as cultural food proscriptions influencing child feeding. Sociodemographic and qualitative data on food beliefs and child-feeding practices were obtained from the primary caretaker of each subject. From pediatric subjects, 24-hour dietary recall data were obtained with the help of the primary caretaker, and capillary blood from a fingerstick was used to detect iron deficiency based on measures of hemoglobin, the zinc protoporphyrin-to-heme ratio, C-reactive protein, and transferrin receptor. With an overall prevalence of 31.2%, iron deficiency was found to be associated with dietary iron intakes constrained by diverse economic, cultural, and environmental factors among Rendille children. In Karare, where children's iron intake approached recommended levels, iron deficiency was found to be attributable to low bioavailability of iron (only 4.3% of total iron intake), rather than low dietary intake per se. By contrast, in Korr the average daily iron intake was estimated at only 65% of recommended allowances, indicating that iron deficiency was the outcome not merely of low bioavailability, but rather of overall inadequate iron intake. Sociodemographic analysis showed a significant interaction between sex and economic status, revealing that girls in economically sufficient households were 2.4 times as likely to have iron deficiency as boys. This difference in risk parallels culturally defined gender-based proscriptions for child feeding: girls are believed to benefit from "soft foods," including rice, maize porridge, and tea, whereas boys benefitfrom "hard foods," including meat, blood, and beans. Consequently, in households economically able to purchase iron-rich foods, these foods are being preferentially fed to boys. Economic development may result in improved iron status for boys, but it will be unlikely to benefit girls in the absence of a dietary modification intervention. A modification of culturally acceptable "soft foods" to include iron-rich foods may provide a sustainable approach to controlling and preventing iron deficiency in this population. PMID:15810798

Shell-Duncan, Bettina; McDade, Thomas

2005-03-01

390

Investigations of Arsenic and Iron Interactions in Environmental Systems Using Synchrotron Radiation Techniques  

NASA Astrophysics Data System (ADS)

Understanding the reactions of arsenic with iron oxide is of critical importance to predicting the environmental cycling and bioavailability of this toxic element. Arsenic is strongly adsorbed on most of the common iron oxide surfaces such as hydrous iron oxide (ferrihydrite), goethite, and lepidocrocite. In addition to surface binding reactions, co-precipitation of arsenic with iron oxide also removes dissolved arsenic from solution. We investigated arsenic binding to iron oxide in a variety of different environmentally relevant systems including batch reactions with synthetic Fe(III) oxides, flow-through column experiments with corroding zero-valent iron as a groundwater remediation material, and sequestration during formation of an Fe(III) precipitate (plaque) on the root surfaces of two aquatic plants (Phalaris arundinacea (reed canarygrass) and Typha latifolia (cattail)). The mechanisms of arsenic binding were investigated using X-ray absorption spectroscopy and X-ray fluorescence microtomography. Arsenate (As(V)) and arsenite (As(III)) form inner-sphere surfaces complexes on ferrihydrite, goethite, and lepidocrocite with As-Fe inter-atomic distances indicative of predominantly bidentate binuclear complexes. Zero-valent iron corrosion causes in-situ Fe(III) oxide formation and both As(V) and As(III) are strongly adsorbed and occluded by the mixed Fe(III) oxide products. Iron plaque of both P. arundinacea and T. latifolia consisted predominantly of ferrihydrite with lesser amounts of goethite and minor levels of siderite. X-ray fluorescence microtomography results suggested that root surface arsenic generally corresponded to regions of enhanced Fe levels.

Manning, B. A.; Hansel, C. M.; Fendorf, S. E.

2002-12-01

391

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 ...

392

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...

393

Long Term Effect of Biotic Reductive Dechlorination on Permeable Treatment Walls  

Microsoft Academic Search

Increased, reactivity is a potentially important phenomena with respect to the cost effectiveness of zero-valent iron permeable barriers. A column study followed by batch experiments using microcosms was performed to analyze biotic reactions and their impact on kinetic reaction rates. In the biotic iron column study ethylene formation as a by-product of the TCE degradation was decreasing gradually after 200

Hala A. Sfeir; A. Randall; D. Reinhart; C. Clausen; C. Geiger

394

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 ...

395

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 ...

396

Performance of a zerovalent iron reactive barrier for the treatment of arsenic in groundwater: Part 1. Hydrogeochemical studies  

NASA Astrophysics Data System (ADS)

Developments and improvements of remedial technologies are needed to effectively manage arsenic contamination in groundwater at hazardous waste sites. In June 2005, a 9.1 m long, 14 m deep, and 1.8 to 2.4 m wide (in the direction of groundwater flow) pilot-scale permeable reactive barrier (PRB) was installed at a former lead smelting facility, located near Helena, Montana (USA). The reactive barrier was designed to treat groundwater contaminated with moderately high concentrations of both As(III) and As(V). The reactive barrier was installed over a 3-day period using bio-polymer slurry methods and modified excavating equipment for deep trenching. The reactive medium was composed entirely of granular iron which was selected based on long-term laboratory column experiments. A monitoring network of approximately 40 groundwater sampling points was installed in July 2005. Monitoring results indicate arsenic concentrations > 25 mg L - 1 in wells located hydraulically upgradient of the PRB. Of 80 groundwater samples collected from the pilot-PRB, 11 samples exceeded 0.50 mg As L - 1 ; 62 samples had concentrations of arsenic at or below 0.50 mg L - 1 ; and, 24 samples were at or below the maximum contaminant level (MCL) for arsenic of 0.01 mg L - 1 . After 2 years of operation, monitoring points located within 1 m of the downgradient edge of the PRB showed significant decreases in arsenic concentrations at depth intervals impacted by the emplaced zerovalent iron. This study indicates that zerovalent iron can be effectively used to treat groundwater contaminated with arsenic given appropriate groundwater geochemistry and hydrology. The study also further demonstrates the shortcomings of hanging-wall designs. Detailed subsurface characterization data that capture geochemical and hydrogeologic variability, including a flux-based analysis, are needed for successful applications of PRB technology for arsenic remediation.

Wilkin, Richard T.; Acree, Steven D.; Ross, Randall R.; Beak, Douglas G.; Lee, Tony R.

2009-04-01

397

Advanced hydraulic fracturing methods to create in situ reactive barriers  

SciTech Connect

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.

Murdoch, L. [FRX Inc., Cincinnati, OH (United States)]|[Clemson Univ., SC (United States). Dept. of Geological Sciences; Siegrist, B.; Meiggs, T. [Oak Ridge National Lab., TN (United States)] [and others

1997-12-31

398

Application of a montmorillonite clay modified with iron in photo-Fenton process. Comparison with goethite and nZVI.  

PubMed

Iron pillared clay (Fe-PILC) was prepared from a montmorillonite and was characterized by scanning electron microscopy and X-ray fluorescence. Fe-PILC catalytic activity was evaluated in photo-Fenton processes applied to the degradation of 2-clorophenol. Different catalyst loads were assayed. The Fe-PILC allowed almost complete degradation of the contaminant. An increase in the contaminant degradation rate was observed, following leaching of iron during catalytic assays, which suggest the existence of a homogeneous photo-Fenton mechanism. The catalytic performance of the Fe-PILC was compared with that for goethite and zero valent iron nanoparticles. Differences were found regarding the achieved degradation levels, the efficiency in oxidant consumption, and the extension of iron leaching. PMID:24604272

De León, María A; Sergio, Marta; Bussi, Juan; Ortiz de la Plata, Guadalupe B; Cassano, Alberto E; Alfano, Orlando M

2015-01-01

399

Evaluation of Geochemical Processes Affecting Uranium Sequestration and Longevity of Permeable Reactive Barriers for Groundwater Remediation  

NASA Astrophysics Data System (ADS)

Development of effective remediation techniques for protecting existing drinking water supplies and for mitigating existing contamination problems requires evaluating both the contaminant sequestration processes and the secondary reactions affecting the long term stability of contaminant attenuation. Permeable reactive barriers (PRB) provide a means for passive remediation of dissolved groundwater contaminants and may be an effective strategy for remediation of uranium (U) groundwater contamination provided that long term stability of the sequestered U can be achieved for the geochemical conditions of the aquifer expected subsequent to remediation. Understanding the chemical reaction mechanisms resulting in U uptake and PRB performance are critical to evaluating the potential for release of sequestered U and for improved design of remediation devices. We are using synchrotron X-ray techniques to investigate U sequestration reaction mechanisms and biogeochemical processes in PRB materials recovered from a 9-year field demonstration of zero-valent iron (ZVI) and bone char apatite PRBs in a U contaminated aquifer near Fry Canyon, Utah. X-ray microprobe mapping of iron phases shows that extensive secondary precipitation of mackinawite, siderite and aragonite in the ZVI PRB has resulted from ZVI corrosion coupled with microbial sulfate reduction. Bulk U-EXAFS measurements and micron-scale U-oxidation state mapping indicates that U removal occurs largely by reduction and precipitation of a UO2-like U(IV) phase on the ZVI surfaces, and that the sequestered U is often buried by the secondary Fe precipitates. These findings are significant to the efficacy of ZVI PRBs for remediation of U and other contaminants in that the ongoing secondary phase precipitation cements grains and fills internal porosity resulting in the observed decreased PRB permeability and limits subsequent U removal, but likely limits oxidative remobilization of U. In the bone char apatite PRB, elevated levels of U uptake were observed at up to 20-times above the maximum for U(VI) sorption by surface complexation expected for this material. XAS measurements show that the sequestered U is predominantly in the +4 oxidation state, instead of +6, indicating a reduction process. Bulk U-EXAFS is consistent with the reduced U(IV) occurring as a sorbed species instead of forming biogenic urananite, and thus may be more likely to undergo re-oxidation and mobilization.

Fuller, C. C.; Webb, S.; Bargar, J.; Naftz, D. L.

2009-12-01

400

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...

401

Laboratory Evaluation of Sulfur Modified Iron for Use as a Filter Material to Treat Agricultural Drainage Waters  

NASA Astrophysics Data System (ADS)

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.

Allred, B. J.

2009-12-01

402

Thermally Evaporated Iron (Oxide) on an Alumina Barrier Layer, by XPS  

SciTech Connect

We report the XPS characterization of a thermally evaporated iron thin film (6 nm) deposited on an Si/SiO_2/Al_2O_3 substrate using Al Ka X-rays. An XPS survey spectrum, narrow Fe 2p scan, narrow O 1s, and valence band scan are shown.

Madaan, Nitesh; Kanyal, Supriya S.; Jensen, David S.; Vail, Michael A.; Dadson, Andrew; Engelhard, Mark H.; Linford, Matthew R.

2013-09-06

403

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

NASA Astrophysics Data System (ADS)

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.

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

2014-11-01

404

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...

405

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 ...