Use Of Zero-valent Iron Research Articles

Groundwater treatment with the use of zero-valent iron in the permeable reactive barrier technology

The industrial dumping sites located in the southern provinces of Poland pollute groundwaters with metals. In the article, the possibility of groundwater (polluted by metals) treatment with the use of Permeable Reactive Barrier Technology has been presented. In this technology, the contaminants are removed from the aquifer by a flow of the groundwater through a PRB filled with a special reactive material. The wastewater (which simulated groundwater) circulated through the column filled with zero-valent iron in the laboratory tests. During the tests, the treatment processes proceeded. Chromium, copper, nickel, cobalt, lead, cadmium and zinc, occurring in the water as cations and anions, have been removed in the iron bed. The rapid metal removal has likely occurred due to the reduction and precipitation/coprecipitation and/or due to adsorption onto the iron metal surface or/and onto the iron corrosion products. Barium Ba was the only metal, which has not been removed from the wastewater in the column. A rapid decrease of the redox potential and oxygen concentration as well as an increases of the pH value and stabilizations have also been observed during the flow of water through the column. Due to the Fe/Fe half reaction during the treatment processes, the iron concentration has increased as well.

Remediation of 4-nonylphenol in aqueous solution by using free radicals generated by the oxidative reactions.

IntroductionThis study relates to use of zerovalent iron to generate hydroxyl free radicals and undergo subsequent oxidation to destroy 4-nonylphenol (NP) by mild process in aqueous solution and activation of oxygen gas (O2) at room temperature. This technology is based on a novel oxidative mechanism mediated by zerovalent iron rather than commonly used reduction mechanism.Materials and methodsA laboratory scale device consisting of a 250 ml pyrex serum vials fixed to a Vortex agitator was used. Different amounts of zerovalent iron powder (ZVI; 1, 10, and 30 g/l) at pH 4 and room temperature with bubbling of oxygen gas were investigated.Results and conclusionExperiments showed an observed degradation rate k (obs) directly proportional to the amount of iron. 4-Nonylphenol degradation reactions demonstrated first-order kinetics with a half-life of about 10.5 ± 0.5 and 3.5 ± 0.2 min when experiments were conducted at [ZVI] = 1 and 30 g/l respectively. Three analytical techniques were employed to monitor 4-nonylphenol degradation and mineralization: (1) spectrofluorimetry; (2) high-performance liquid chromatography; (3) total organic carbon meter (TOC meter). Results showed a complete disappearance of 4-nonylphenol after 20 min of contact with ZVI. The intermediate by-products of the reaction were not identified but the disappearance of NP was monitored by the three above-mentioned techniques.

Sulfate reduction in groundwater: characterization and applications for remediation

Sulfate is ubiquitous in groundwater, with both natural and anthropogenic sources. Sulfate reduction reactions play a significant role in mediating redox conditions and biogeochemical processes for subsurface systems. They also serve as the basis for innovative in situ methods for groundwater remediation. An overview of sulfate reduction in subsurface environments is provided, along with a brief discussion of characterization methods and applications for addressing acid mine drainage. We then focus on two innovative, in situ methods for remediating sulfate-contaminated groundwater, the use of zero-valent iron and the addition of electron-donor substrates. The advantages and limitations associated with the methods are discussed, with examples of prior applications.

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

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).

Hexavalent Chromium Reduction with Zero-Valent Iron (ZVI) in Aquatic Systems

Hexavalent chromium is a heavy metal used in a variety of industrial applications which is highly toxic to humans, animals, plants and microorganisms. Moreover, it is a well-established human carcinogen by the inhalation route of exposure and a possible human carcinogen by the oral route of exposure. Therefore, it should be removed from contaminated waters. Its reduction to trivalent chromium can be beneficial because a more mobile and more toxic chromium species is converted to a less mobile and less toxic form. During the last two decades, there has been important interest in using zero-valent iron (ZVI) as a Cr(VI)-reducing agent. A considerable volume of research has been carried out in order to investigate the mechanism and kinetics of Cr(VI) reduction with ZVI, as well as the influence of various parameters controlling the reduction efficiency. Therefore, the purpose of this review was to provide updated information regarding the developments and innovative approaches in the use of ZVI for the treatment of Cr(VI)-polluted waters.

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

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 ( t 1/2) 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.

Applying an electric field in a built-in zero valent iron – Anaerobic reactor for enhancement of sludge granulation

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

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

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.

Microwave-hydrothermal decomposition of perfluorooctanoic acid in water by iron-activated persulfate oxidation

The microwave-hydrothermal decomposition of persistent and bioaccumulative perfluorooctanoic acid (PFOA) in aqueous solution using persulfate activated by zero-valent iron (ZVI) at 60 and 90 °C was examined. The results of laboratory study reveal that when PFOA is treated with 5 mM persulfate (PS) and ZVI at 90 °C for 2 h, 67.6% of PFOA is effectively decomposed to form shorter-chain perfluorinated carboxylic acids (PFCAs) and fluoride ions, with 22.5% defluorination efficiency. Introducing ZVI into the PFOA solution with PS addition will lead to synergetic effect that accelerates the PFOA decomposition rate, and reduces the reaction time. ZVI not only decomposes PFOA, but also releases ferrous ions to lower the activation energy of PS while forming sulfate free radicals at a lower reaction temperature. The combined use of ZVI and persulfate will lead to significant savings in energy consumption and reduction of process time.

Remediating dinoseb-contaminated soil with zerovalent iron

Dinoseb, a dinitroherbicide, was once commonly used in aerial crop dusting of agronomic crops in the western United States. Widespread use combined with improper disposal practices at rural air strips has contaminated numerous sites. Our objective was to determine if zerovalent iron (Fe 0) could remediate dinoseb-contaminated soil. This was accomplished by conducting a series of batch experiments where we first determined if Fe 0 could remove dinoseb in aqueous solutions, then in contaminated soil slurries, and finally, in unsaturated soil microcosms (25 °C, θ g = 0.30 kg H 2O kg −1). Results showed quantitative dinoseb removal in the presence of Fe 0 in all three media (aqueous solutions, soil slurries, moist soils) and that removal increased by including either ferrous or aluminum sulfate with the iron treatment. Incubating contaminated soils with Fe 0 or Fe 0 plus salts (FeSO 4 or Al 2(SO 4) 3) resulted in 100% removal of dinoseb within 7 d. Liquid chromatography/mass spectrometry (LC/MS) analysis of degradation products showed the transformations imposed by the iron treatments were reduction of one or both nitro groups to amino groups. These amino degradation products were further transformed to quinonimine and benzoquinone and did not persist. These results support the use of zerovalent iron for on-site treatment of dinoseb-contaminated soil.

Coupled acidification and ultrasound with iron enhances nitrate reduction

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 (Fe 0) is suggested. The formation of passivating scales on Fe 0 over time may limit the long-term reduction potential of Fe 0. The aim of this study was to investigate the effect of ultrasound and pH on the destruction of passive oxide film. Batch tests were conducted in a specially designed protocol using ultrasound, and changing iron (commercial iron powder of micro-scale grain size) loading and pH. The results showed deactivation of the degradation process by Fe 0 with combined ultrasound/iron system and with ultrasound alone. However, the degradation rate increases with decrease in pH. The degradation rate was 45% for pH 2 and 20% for pH 4. The combination of iron, acidification, and ultrasound showed excellent degradation efficiency, and the degradation rate was 99%. Acidification could destroy passive oxide film and activate iron, thus, hastening the reaction between Fe 0 and nitrate. Ultrasound was helpful in destroying or preventing the formation of passive oxide film under acidification.

Reduction of nitrate by nanoscale zero-valent iron supported on mesoporous silica beads

The use of zero-valent iron (ZVI) represents one of the latest innovative technologies for groundwater remediation. The reactivity of ZVI is enhanced when the particle size is in the nanometer range. However, nanoscale ZVI has limited field applications for in-situ groundwater remediation such as permeable reactive barriers due to its powdery form. Therefore, a method of adhering nanoparticles on a supporting material was suggested. In this paper, functionalized mesoporous silica beads were created using 3-mercaptopropyltrimethoxy silica, tetrabutyl orthosilicate, and cetyltrimethyl ammonium bromide, and their physical and chemical characteristics were measured. The highly active ZVI nanoparticles were adhered on these mesoporous silica beads. The reactivity of the resulting material was tested using nitrate solution. The reductive reaction of nitrate indicated that the degradation of nitrate appeared to be pseudo-first order with a high reaction rate constant of 0.1619 h-1. The reaction constant decreased to 0.0122 h-1 after 3 h of experiment due to mass transfer limitation. The higher dose of the supported nanosized ZVI increased the removal rate as well as the removal efficiency of nitrate.

Zero-valent iron treatment of RDX-containing and perchlorate-containing wastewaters from an ammunition-manufacturing plant at elevated temperatures

The use of zero-valent iron for treating wastewaters containing RDX and perchlorate from an army ammunition plant (AAP) in the USA at elevated temperatures and moderately elevated temperature with chemical addition was evaluated through batch and column experiments. RDX in the wastewater was completely removed in an iron column after 6.4 minutes. Increasing the temperature to 75 degrees C decreased the required retention time to 2.1 minutes for complete RDX removal. Perchlorate in the wastewater was completely removed by iron at an elevated temperature of 150 degrees C in batch reactors in 6 hours without pH control. Significant reduction of perchlorate by zero-valent iron was also achieved at a more moderate temperature (75 degrees C) through use of a 0.2 M acetate buffer. Based on the evaluation results, we propose two innovative processes for treating RDX-containing and perchlorate-containing wastewaters: a temperature and pressure-controlled batch iron reactor and subsequent oxidation by existing industrial wastewater treatment plant; and reduction by consecutive iron columns with heating and acid addition capabilities and subsequent oxidation.

Microbial reduction of perchlorate with zero-valent iron

Microbial reduction of perchlorate in the presence of zero-valent iron was examined in both batch and column reactors to assess the potential of iron as the electron donor for biological perchlorate reduction process. Iron-supported mixed cultures completely removed 65 mg/L of perchlorate in batch reactors in 8 days. The removal rate was similar to that observed with hydrogen gas (5%) and acetate (173 mg/L) as electron donors. Repeated spiking of perchlorate to batch reactors containing iron granules and microorganisms showed that complete perchlorate reduction by the iron-supported culture was sustained over a long period. Complete removal of perchlorate by iron-supported anaerobic culture was also achieved in a bench-scale iron column with a hydraulic residence time of 2 days. This study demonstrated the potential applicability of zero-valent iron as a source of electrons for biological perchlorate reduction. Use of zero-valent iron may eliminate the need to continually supply electron donors such as organic substrates or explosive hydrogen gas. In addition, iron is inexpensive, safe to handle, and does not leave organic residuals in the treated water.

Kinetics of RDX degradation by zero-valent iron (ZVI)

Hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) is a common groundwater contaminant at military facilities. The current research has been conducted to evaluate the use of zero-valent iron (ZVI) for the remediation of water contaminated with RDX. RDX was found to degrade rapidly in the presence of ZVI. The observed first-order kinetic constant for RDX reduction follows an enzymatic-like kinetic model with respect to the ZVI concentration. At low ZVI concentrations, RDX reduction follows pseudo first order kinetics with respect to ZVI concentration; while at high ZVI concentrations the RDX reduction is zero-order. Nitroso compounds (MNX, DNX, and TNX), nitrate, nitrite and nitrous oxide were identified as the main by-products for the RDX reduction by ZVI. The nitroso compounds were found to undergo reduction by ZVI.

Zero-Valent Iron for Water Treatment

The use of zero-valent iron in the treatment of hazardous water contaminants is reviewed. The review concentrates on experimental procedures employed in the investigation of a range of applications for zero -valent iron and the efficacy of the processes. Investigations reviewed include those performed with halogenated aliphatic compounds, halogenated aromatic compounds, nitro-aromatic organic compounds, and high-valency toxic metals. Experiments employing bimetallic and cementation reductants as well as zero-valent iron alone are covered. The need for zero-valent iron technology is discussed, as is the need for more rigorous investigation of operational parameters. Despite a paucity of information from the literature it has been shown that efficacy is greatest for well-mixed batch or continuous column systems employing neutral to acidic pH and a high specific surface area of iron. The literature also reveals a need to focus future work on enhancing the chemical reaction taking place on the iron surface in order to enhance the rate of reductive remediation.

Removal of Halogenated Organic Compounds in Landfill Gas by Top Covers Containing Zero-Valent Iron

Transformation of gaseous CCl3F and CCl4 by zero-valent iron was studied in systems unsaturated with water under anaerobic conditionsin an N2 gas and in a landfill gas atmosphere. The transformation was studied in batch as well as flow-through column tests. In both systems, the transformation process of the compounds was pseudo-first-order. Transformation rate constants, referring to the water phase and normalized to 1 m2 iron surface/mL, of up to 1100 mL m-2 h-1 (batch) and 200 mL m-2 h-1 (flow-through) were found. The transformation was strongly dependent on pH and the presence of oxygen. During continuous aerobic conditions, the transformation of CCl3F decreased toward zero. Model calculations show that use of zero-valent iron in landfill top covers is a potential treatment technology for emission reduction of halogenated trace compounds from landfills.