Perchlorate reduction by autotrophic bacteria attached to zerovalent iron in a flow-through reactor

Biological reduction of perchlorate by autotrophic microorganisms attached to zerovalent iron (ZVI) was studied in flow-through columns. The effects of pH, flow rate, and influent perchlorate and nitrate concentrations on perchlorate reduction were investigated. Excellent perchlorate removal performance (> or = 99%) was achieved at empty bed residence times (EBRTs) ranging from 0.3 to 63 h and an influent perchlorate concentration of 40-600 microg L(-1). At the longest liquid residence times, when the influent pH was above 7.5, a significant increase of the effluent pH was observed (pH > 10.0), which led to a decrease of perchlorate removal. Experiments at short residence times revealed that the ZVI column inoculated with local soil (Colton, CA) containing a mixed culture of denitrifiers exhibited much better performance than the columns inoculated with Dechloromonas sp. HZ for reduction of both perchlorate and nitrate. As the flow rate was varied between 2 and 50 mL min(-1), corresponding to empty bed contact times of 0.15-3.8 h, a maximum perchlorate elimination capacity of 3.0 +/- 0.7 g m(-3) h(-1) was obtained in a soil-inoculated column. At an EBRT of 0.3 h and an influent perchlorate concentration of 30 microg L(-1), breakthrough (> 6 ppb) of perchlorate in the effluent did not occur until the nitrate concentration in the influent was 1500 times (molar) greater than that of perchlorate. The mass of microorganisms attached on the solid ZVI/sand was found to be 3 orders of magnitude greater than that in the pore liquid, indicating that perchlorate was primarily reduced by bacteria attached to ZVI. Overall, the process appears to be a promising alternative for perchlorate remediation.     

Polyoxometalate-enhanced oxidation of organic compounds by nanoparticulate zero-valent iron and ferrous ion in the presence of oxygen

In the presence of oxygen, organic compounds can be oxidized by zerovalent 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 the solution pH. Under acidic conditions, POM mediates the electron transfer from nanoparticulate zerovalent 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) is exposed to oxygen in the presence of silica-immobilized POM.     

Temperature programmed reduction for measurement of oxygen content in nanoscale zero-valent iron

Nanoscale zerovalent iron (nZVI) has increasingly been used for environmental remediation and in toxic waste treatment. Most applications exploit its large surface area and high reactivity, the latter being a function of zerovalent iron content. In this work, temperature programmed reduction was applied to measure oxygen in nZVI. Iron oxides in nZVI were reduced by hydrogen to form metallic iron and water, which was then measured with an online mass spectrometer to determine oxygen content of the sample. For fresh nZVI prepared by sodium borohydride reduction of iron salts, average oxygen content was 8.21%. Total iron content was approximately 90.35% by the method of acid digestion; Fe(III) content was estimated at 14.37%, and that of zerovalent iron [Fe(0)] at 75.98%. The oxygen content quickly increased to 26.14% after purging with oxygen for four hours. Several other techniques were also used to characterize the iron nanoparticles. High resolution TEM provided direct evidence of the oxide shell structure and indicated that the shell thickness was predominantly in the range of 2-4 nm. The surface elemental composition was determined from high-resolution X-ray photoelectron spectroscopy. The nZVI oxygen content results fill a knowledge gap on nZVI composition.     

Enhanced perchloroethylene reduction in column systems using surfactant-modified zeolite/zero-valent iron pellets

Surfactant- (hexadecyltrimethylammonium, HDTMA) modified zeolite (SMZ)/zero-valent iron (ZVI) pellets having high hydraulic conductivity (9.7 cm s(-1)), high surface area (28.2 m2 g(-1)), and excellent mechanical strength were developed. Laboratory column experiments were conducted to evaluate the performance of the pellets for perchloroethylene (PCE) sorption/reduction under dynamic flow-through conditions. PCE reduction rates with the surfactant-modified pellets (SMZ/ZVI) were three times higher than the reduction rates with the unmodified pellets (zeolite/ZVI). We speculate that enhanced sorption of PCE directly onto iron surface by iron-bound HDTMA and/or an increased local PCE concentration in the vicinity of iron surface due to sorption of PCE by SMZ contributed to the enhanced PCE reduction by the SMZ/ZVI pellets. Trichloroethylene and cis-dichloroethylene production during PCE reduction increased with the surfactant-modified pellets, indicating that the surfactant modification may have favored hydrogenolysis over beta-elimination. PCE reduction rate constants increased as the travel velocity increased from 0.5 to 1.9 m d(-1), suggesting that the reduction of PCE in the column systems was mass transfer limited.     

Chromium(VI) reduction kinetics by zero-valent iron in moderately hard water with humic acid: iron dissolution and humic acid adsorption

In zerovalent iron treatment systems, the presence of multiple solution components may impose combined effects that differ from corresponding individual effects. The copresence of humic acid and hardness (Ca2+/Mg2+) was found to influence Cr(VI) reduction by Feo and iron dissolution in a way different from their respective presence in batch kinetics experiments with synthetic groundwater at initial pH 6 and 9.5. Cr(VI) reduction rate constants (k(obs)) were slightly inhibited by humic acid adsorption on iron filings (decreases of 7-9% and 10-12% in the presence of humic acid alone and together with hardness, respectively). The total amount of dissolved Fe steadily increased to 25 mg L(-1) in the presence of humic acid alone because the formation of soluble Fe-humate complexes appeared to suppress iron precipitation. Substantial amounts of soluble and colloidal Fe-humate complexes in groundwater may arouse aesthetic and safety concerns in groundwater use. In contrast, the coexistence of humic acid and Ca2+/Mg2+ significantly promoted aggregation of humic acid and metal hydrolyzed species, as indicated by XPS and TEM analyses, which remained nondissolved (>0.45 microm) in solution. These metal-humate aggregates may impose long-term impacts on PRBs in subsurface settings.     

Ligand-enhanced reactive oxidant generation by nanoparticulate zero-valent iron and oxygen

The reaction of zero-valent iron or ferrous iron with oxygen produces reactive oxidants capable of oxidizing organic compounds. However, the oxidant yield in the absence of ligands is too low for practical applications. The addition of oxalate, nitrilotriacetic acid (NTA), or ethylenediaminetetraacetic acid (EDTA) to oxygen-containing solutions of nanoparticulate zero-valent iron (nZVI) significantly increases oxidant yield, with yields approaching their theoretical maxima near neutral pH. These ligands improve oxidant production by limiting iron precipitation and by accelerating the rates of key reactions, including ferrous iron oxidation by oxygen and hydrogen peroxide. Product yields indicate that the oxic nZVI system produces hydroxyl radical (OH*) over the entire pH range in the presence of oxalate and NTA. In the presence of EDTA, probe compound oxidation is attributed to OH under acidic conditions and a mixture of OH* and ferryl ion (Fe[IV]) at circumneutral pH.     

Quantification of the oxidizing capacity of nanoparticulate zero-valent iron

Addition of nanoparticulate zero-valent iron (nZVI) to oxygen-containing water results in oxidation of organic compounds. To assess the potential application of nZVI for oxidative transformation of organic contaminants, the conversion of benzoic acid (BA) to p-hydroxybenzoic acid (p-HBA) was used as a probe reaction. When nZVI was added to BA-containing water, an initial pulse of p-HBA was detected during the first 30 min, followed by the slow generation of additional p-HBA over periods of at least 24 h. The yield of p-HBA increased with increasing BA concentration, presumably due to the increasing 'ability of BA to compete with alternate oxidant sinks, such as ferrous iron. At pH 3, maximum yields of p-HBA during the initial phase of the reaction of up to 25% were observed. The initial rate of nZVI-mediated oxidation of BA exhibited a marked reduction at pH values above 3. Despite the decrease in oxidant production rate, p-HBA was observed during the initial reaction phase at pH values up to 8. Competition experiments with probe compounds expected to exhibit different affinities for the nZVI surface (phenol, aniline, o-hydroxybenzoic acid, and synthetic humic acids) indicated relative rates of reaction that were similar to those observed in competition experiments in which hydroxyl radicals were generated in solution. Examination of the oxidizing capacity of a range of Fe0 particles reveals a capacity in all cases to induce oxidative transformation of benzoic acid, but the high surface areas that can be achieved with nanosized particles renders such particles particularly effective oxidants.     

Inactivation of MS2 coliphage by ferrous ion and zero-valent iron nanoparticles

This study demonstrates the inactivation of MS2 coliphage (MS2) by nano particulate zerovalent iron (nZVI) and ferrous ion (Fe[II]) in aqueous solution. For nZVI, the inactivation efficiency of MS2 under air-saturated conditions was greater than that observed under deaerated conditions, indicating that reactions associated with the oxidation of nZVI were mainly responsible for the MS2 inactivation. Under air-saturated conditions, the inactivation efficiency increased with decreasing pH for both nZVI and Fe(II), associated with the pH-dependent stability of Fe(II). Although the Fe(II) released from nZVI appeared to contribute significantly to the virucidal activity of nZVI, several findings suggest that the nZVI surfaces interacted directly with the MS2 phages, leading to their inactivation. First, the addition of 1,10-phenanthroline (a strong Fe(II)-chelating agent) failed to completely block the inactivation of MS2 by nZVI. Second, under deaerated conditions, a linear dose-log inactivation curve was still observed for nZVI. Finally, ELISA analysis indicated that nZVI caused more capsid damage than Fe(II).     

Removal of arsenic(III) from groundwater by nanoscale zero-valent iron

Nanoscale zero-valent iron (NZVI) was synthesized and tested for the removal of As(III), which is a highly toxic, mobile, and predominant arsenic species in anoxic groundwater. We used SEM-EDX, AFM, and XRD to characterize particle size, surface morphology, and corrosion layers formed on pristine NZVI and As(III)-treated NZVI. AFM results showed that particle size ranged from 1 to 120 nm. XRD and SEM results revealed that NZVI gradually converted to magnetite/maghemite corrosion products mixed with lepidocrocite over 60 d. Arsenic(III) adsorption kinetics were rapid and occurred on a scale of minutes following a pseudo-first-order rate expression with observed reaction rate constants (K(obs)) of 0.07-1.3 min(-1) (at varied NZVI concentration). These values are about 1000x higher than K(obs) literature values for As(III) adsorption on micron size ZVI. Batch experiments were performed to determine the feasibility of NZVI as an adsorbent for As(III) treatment in groundwater as affected by initial As(III) concentration and pH (pH 3-12). The maximum As(III) adsorption capacity in batch experiments calculated by Freundlich adsorption isotherm was 3.5 mg of As(III)/g of NZVI. Laser light scattering (electrophoretic mobility measurement) confirmed NZVI-As(III) inner-sphere surface complexation. The effects of competing anions showed HCO3-, H4SiO4(0), and H2P04(2-) are potential interferences in the As(III) adsorption reaction. Our results suggest that NZVI is a suitable candidate for both in-situ and ex-situ groundwater treatment due to its high reactivity.     

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

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

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

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.     

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

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

Field demonstration of DNAPL dehalogenation using emulsified zero-valent iron

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.     

Bactericidal effect of zero-valent iron nanoparticles on Escherichia coli

Zero-valent iron nanoparticles (nano-Fe0) in aqueous solution rapidly inactivated Escherichia 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 x h). 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.     

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

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.     

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

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.     

Dissolution and reduction of magnetite by bacteria

Magnetite (Fe3O4) is an iron oxide of mixed oxidation state [Fe(II), Fe(III)] that contributes largely to geomagnetism and plays a significant role in diagenesis in marine and freshwater sediments. Magnetic data are the primary evidence for ocean floor spreading and accurate interpretation of the sedimentary magnetic record depends on an understanding of the conditions under which magnetite is stable. Though chemical reduction of magnetite by dissolved sulfide is well known, biological reduction has not been considered likely based upon thermodynamic considerations. This study shows that marine and freshwater strains of the bacterium Shewanella putrefaciens are capable of the rapid dissolution and reduction of magnetite, converting millimolar amounts to soluble Fe(II)in a few days at room temperature. Conditions under which magnetite reduction is optimal (pH 5-6, 22-37 degrees C) are consistent with an enzymatic process and not with simple chemical reduction. Magnetite reduction requires viable cells and cell contact, and it appears to be coupled to electron transport and growth. In a minimal medium with formate or lactate as the electron donor, more than 10 times the amount of magnetite was reduced over no carbon controls. These data suggest that magnetite reduction is coupled to carbon metabolism in S. putrefaciens. Bacterial reduction rates of magnetite are of the same order of magnitude as those estimated for reduction by sulfide. If such remobilization of magnetite occurs in nature, it could have a major impact on sediment magnetism and diagenesis.     

Oxidative degradation of the carbothioate herbicide, molinate, using nanoscale zero-valent iron

Degradation of the carbothiolate herbicide, molinate, has been investigated in oxic solutions containing nanoscale zero-valent iron particles and found to be effectively degraded by an oxidative pathway. Both ferrous iron and superoxide (or, at pH < 4.8, hydroperoxy) radicals appearto be generated on corrosion of the zero-valent iron with resultant production of strongly oxidizing entities capable of degrading the trace contaminant.     

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

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.