EDTA degradation induced by oxygen activation in a zerovalent iron/air/water system

A method for the removal of ethylenediaminetetraacetic acid (EDTA) at room temperature and 1 atm is demonstrated. EDTA (1 mM, 50 mL) containing 2.5 g of granular zerovalent iron (ZVI) (20-40 mesh) was degraded in 2.5 h. Using a recently developed form of O2 activation, reactive oxygen species are generated in situ, resulting in the degradation of EDTA when complexed with FeII. ESI-MS measurements indicate that degradation of EDTA yields low-molecular carboxylic acids. The presence of oxygen is crucial: the observed pseudo-first-order rate constants for EDTA removal are kobs = 1.02 h(-1) (kSA = 1.85 +/- 0.046 L h(-1) m(-2)) and kobs = 0.04 h(-1) (kSA = 0.00724 +/- 0.002 L h(-1) m(-2)) under air and under N2 purge, respectively. kSA represents surface area normalized rate constants. Large excesses of EDTA in the reaction mixture slowthe rate of degradation. Increasing the concentration of EDTA from 1.0 to 10.0 mM while holding all other parameters constant gave observed rates of kobs = 1.02 +/- 0.26 h(-1) (kSA = 1.85 +/- 0.046 L h(-1) m(-2)) and kobs = 0.044 +/- 0.01 h(-1) (kSA = 0.00796 +/- 0.002 L h(-1) m(-2)), respectively. The rate-limiting step is determined to be homogeneous oxygen activation.     

Green rust and iron oxide formation influences metolachlor dechlorination during zerovalent iron treatment

Electron transfer from zerovalent iron (Fe0) to targeted contaminants is affected by initial Fe0 composition, the oxides formed during corrosion, and surrounding electrolytes. We previously observed enhanced metolachlor destruction by Fe0 when iron or aluminum salts were present in the aqueous matrix and Eh/pH conditions favored formation of green rusts. To understand these enhanced destruction rates, we characterized changes in Fe0 composition during treatment of metolachlor with and without iron and aluminum salts. Raman microspectroscopy and X-ray diffraction (XRD) indicated that the iron source was initially coated with a thin layer of magnetite (Fe3O4), maghemite (gamma-Fe2O3), and wüstite (FeO). Time-resolved analysis indicated that akaganeite (beta-FeOOH) was the dominant oxide formed during Fe0 treatment of metolachlor. Goethite (alpha-FeOOH) and some lepidocrocite (gamma-FeOOH) formed when Al2(SO4)3 was present, while goethite and magnetite (Fe3O4) were identified in Fe0 treatments containing FeSO4. Although conditions favoring formation of sulfate green rust (GR(II); Fe6(OH)12SO4) facilitated Fe0-mediated dechlorination of metolachlor, only adsorption was observed when GR(II) was synthesized (without Fe0) in the presence of metolachlor and Eh/pH changed to favor Fe(III)oxyhydroxide or magnetite formation. In contrast, dechlorination occurred when magnetite or natural goethite was amended with Fe(II) (as FeSO4) at pH 8 and continued as long as additional Fe(II) was provided. While metolachlor was not dechlorinated by GR(II) itself during a 48-h incubation, the GR(II) provided a source of Fe(II) and produced magnetite (and other oxide surfaces) that coordinated Fe(II), which then facilitated dechlorination.     

Long-term effects of dissolved carbonate species on the degradation of trichloroethylene by zerovalent iron

The effect of different concentrations of total inorganic carbon (TIC) and flow rates on the reactivity of iron metal with trichloroethylene (TCE) was studied in column experiments to verify whether concentration or mass flux of TIC is the major key parameter for barrier performance. First-order rate coefficients (kobs) for TCE degradation vary initially between 0.15 and 0.32 h-' and are positively related to TIC influent concentration. Maximal kobs were reached after 164 and 591 PV, varied between 0.55 and 1.1 h(-1), and were positively correlated to the TIC mass flux, followed by a decrease resulting in values similar to the reference system at the end of the experiments. Enhancement of iron corrosion (0.7 to 3.5 mmol kgFe(-1) d(-1) and formation of gas bubbles during the initial experimental phase were observed and were also positively correlated to TIC mass flux. The higher gas bubble formation probably has a more significant effect on porosity than mineral precipitations in Fe0-systems. The results suggest that higher TIC mass fluxes cause a more pronounced acceleration in CHC degradation, but also a faster inhibition in the longer-term. This faster inhibition has serious implication for the design of funnel and gate systems.     

Chromium-removal processes during groundwater remediation by a zerovalent iron permeable reactive barrier

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 microg L(-1) in groundwater hydraulically upgradient of the PRB to values <1 microg L(-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.     

Understanding soluble arsenate removal kinetics by zerovalent iron media

Zerovalent iron filings have been proposed as a filter medium for removing arsenic compounds from potable water supplies. This research investigated the kinetics of arsenate removal from aqueous solutions by zerovalent iron media. Batch experiments were performed to determine the effect of the iron corrosion rate on the rate of As(V) removal. Tafel analyses were used to determine the effect of the As(V) concentration on the rate of iron corrosion in anaerobic solutions. As(V) removal in column reactors packed with iron filings was measured over a 1-year period of continuous operation. Comparison of As(V) removal by freely corroding and cathodically protected iron showed that rates of arsenate removal were dependent on the continuous generation of iron oxide adsorption sites. In addition to adsorption site availability, rates of arsenate removal were also limited by mass transfer associated with As(V) diffusion through iron corrosion products. Steady-state removal rates in the column reactor were up to 10 times faster between the inlet-end and the first sampling port than between the first sampling port and the effluent-end of the column. Faster removal near the influent-end of the column was due to a faster rate of iron oxidation in that region. The presence of 100 microg/L As(V) decreased the iron corrosion rate by up to a factor of 5 compared to a blank electrolyte solution. However, increasing the As(V) concentration from 100 to 20,000 microg/L resulted in no further decrease in the iron corrosion rate. The kinetics of arsenate removal ranged between zeroth- and first-order with respect to the aqueous As(V) concentration. The apparent reaction order was dependent on the availability of adsorption sites and on the aqueous As(V) concentration. X-ray absorption spectroscopy analyses showed the presence of iron metal, magnetite (Fe3O4), an Fe(III) oxide phase, and possibly an Fe(II,III) hydroxide phase in the reacted iron filings. These mixed valent oxide phases are not passivating and permit sustained iron corrosion and continuous generation of new sites for As(V) adsorption.     

Reductive debromination of polybrominated diphenyl ethers by zerovalent iron

Polybrominated diphenyl ethers (PBDEs) are a new class of global, persistent, and toxic contaminants, which need proper remediation technologies. PBDE degradation in the environment is not well understood. In this study, degradation of PBDEs with zerovalent iron was investigated with six BDEs, substituted with one to 10 bromines. Within 40 days 92% of BDE congener 209 was transformed into lower bromo congeners. During the initial reaction period of BDE 209 (<5 days), hexa- to heptabromo BDEs were the most abundant products, but tetra- to pentabromo congeners were dominant after 2 weeks. The amount of mono- to tribromo BDEs was steadily increased during the experiments. BDEs 28, 47, 66, and 100 also showed a stepwise accumulation of lower bromo congeners. No oxidation products were detected in all experiments. The results showed that a stepwise debromination from n-bromoto (n-1)-bromodiphenyl ethers was the dominant reaction in all congeners. The reaction rate constants of lower bromo BDEs decreased as the number of bromines decreased. The initial reductive debromination rate constants were positively correlated with the heats of formation of BDEs. The preferential accumulation of specific congeners was observed in the experiment with BDEs 28, 47, 66, and 100, where the most abundant products were BDEs 15, 28, 37, and 47, respectively. Reactions proceeded to form more stable and less brominated products that have lower heats of formation. Almost all the possible isomers from a specific parent BDE were found in all the experiments, which was probably due to the small difference of heat of formation between the products (2-5 kcal/mol). Reactions of all congeners proceeded fast at the initial phase (<5 days) followed by a slow reaction. The rate of reductive debromination of BDE 209 was slower with environmentally relevant sulfide minerals (iron sulfide and sodium sulfide). However, the product congener pattern, produced by sulfide mineral catalysis, was nearly similar with that of zerovalent iron treatment. This may be a possible source of lower brominated BDEs in the environment. Debromination of PBDEs by zerovalent iron has high potential values for remediation of PBDEs in the environment.     

Oxidation on zerovalent iron promoted by polyoxometalate as an electron shuttle

Most studies on zerovalent iron (ZVI) were mainly focused on the reductive transformation of halo- or nitrocompounds. Oxidation reactions occurring on ZVI have been recently recognized. In this study, we demonstrate that the oxidation pathways on ZVI can be accelerated by the presence of polyoxometalate (POM: nanosized metaloxygen cluster anion) serving as an electron shuttle. The ions, SiW12O40(4-) and PW12O40(3-), can mediate the electron transfer from the Fe0 surface to 02 while enhancing the production of H2O2, which subsequently initiates the OH radical-mediated oxidation through a Fenton-type reaction. The oxidation reaction was completely quenched by adding methanol as an OH radical-scavenger. On the other hand, PMo12O40(3-) completely inhibited the oxidative degradation by irreversibly scavenging an electron and holding it. We systematically investigated the effects of iron loading, the concentration of POM, and pH on the oxidative degradation kinetics of 4-chlorophenol in the POM-mediated ZVI system. The POM-mediated oxidations on ZVI were additionally tested for 12 organic contaminants and the rates were compared. Their oxidative degradation on ZVI was mostly enhanced in the presence of POM (SiW12O40(4-)). The present study provides a good model system upon which the ZVI-based oxidation technologies can be successfully enhanced and modified for further developments.     

Adsorption of humic acid onto nanoscale zerovalent iron and its effect on arsenic removal

Batch experiments were performed to investigate the feasibility of humic acid (HA) removal by synthetic nanoscale zerovalent iron (NZVI) and its interaction with As(III) and As(V), the most poisonous and abundant of groundwater pollutants. High-resolution transmission electron microscopy (HR-TEM) and X-ray diffraction (XRD) were used to characterize the particle size, surface morphology of the pristine NZVI and HA-treated NZVI (NZVI-HA), and the zero valence state of the pristine NZVI. It was determined that HA was completely removed by NZVI (0.3 g/L) within a few minutes, at a wide range of initial pH values (approximately 3.0-12.0). Fourier transform infrared (FTIR) and laser light scattering (zeta potential measurement) studies confirmed that NZVI-HA forms inner-sphere surface complexation at different initial pH conditions. The effects of competing anions showed that there was complete removal of HA in the presence of 10 mM NO(-3) and SO4(2-) whereas HA removal was observed 0%, 18% and 22% in presence of 10 mM H2PO4(2-), HCO(3-) and H4SiO4(0), respectively. However, the presence of 2 mM CA2+ and Mg2+ enhanced HA removal from 17 mg g(-1) to 76 mg g(-1) and 55 mg g(-1), respectively. Long-term time-resolved studies of XRD and field emission scanning electron microscopy (FE-SEM) with energy-dispersive X-ray (EDX) revealed the formation of various types of new iron oxides (magnetite, maghemite, and lepidocrocites) during the continuous reaction of HA in the presence of water and NZVI at 1, 30, 60, and 90 days. In addition, the surface-area-normalized rate constant (ksa) of adsorption of As(III) and As(V) onto NZVI was reduced in the presence of HA (20 mg L(-1)), from 100% to 43% and 68%, respectively. Our results show the potential use of NZVI in removing HA and its possible effects on arsenic removal during the application of NZVI in groundwater remediation.     

Congener-specific dechlorination of dissolved PCBs by microscale and nanoscale zerovalent iron in a water/methanol solution

Polychlorinated biphenyl (PCB)-contaminated sediments remain a significantthreatto humans and aquatic ecosystems. Dredging and disposal is costly, so viable in situ technologies to dechlorinate PCBs are needed. This study demonstrates that nanoscale zerovalent iron (ZVI) dechlorinates PCBs to lower-chlorinated products under ambient conditions, provides insight into structure-activity relationships between PCB isomers, and compares the reactivity of nanoscale ZVI to that of palladized microscale ZVI. Six PCB congeners were studied (22', 34', 234, 22'35', 22'45', and 33'44') to compare the initial rate of dechlorination of each and to monitor the order in which chlorines are removed. Using 200 g/L of nanoscale ZVI in a 30% MeOH/water mixture, observed surface-area-normalized pseudo-first-order PCB dechlorination rate constants ranged from 1 x 10(-6) to 5.5 x 10(-4) L yr(-1) m(-2) depending on the PCB congener tested. Using 200 g/L of palladized (0.05 wt %) microscale ZVI, surface-area-normalized pseudo-first-order PCB dechlorination rate constants were significantly faster and ranged from 3.8 x 10(-2) to 1.7 x 10(-1) L yr(-1) m(-2), but these rates were not sustainable. For nanoscale ZVI, nonorthosubstituted congeners had faster initial dechlorination rates than orthosubstituted congeners in the same homologue group. Chlorines in the para and meta position were predominantly removed over chlorines in the ortho position, which suggests that more-toxic coplanar PCB congeners are not likely to form from less-toxic noncoplanar, orthosubstituted congeners. Complete dechlorination was not observed over the course of the experiments. PCB dechlorination is rapid enough that nanoscale ZVI may offer novel in situ remedial alternatives for PCB-contaminated sediments.     

Rapid dechlorination of polychlorinated dibenzo-p-dioxins by bimetallic and nanosized zerovalent iron

Polychlorinated dibenzo-p-dioxins and furans (PCDD/Fs), especially the 2,3,7,8-substituted congeners, are extremely toxic, persistent, and recalcitrant to remediation. Dechlorination of PCDD/Fs by zerovalent iron (ZVI) is thermodynamically feasible, but useful rates of reaction have not been previously reported. Here we show that ZVI (both micro- and nanosized ZVI, without palladization) dechlorinates PCDD congeners with four or more chlorines in aqueous systems, but the reaction is too slow to achieve complete dechlorination within a practical period of time. In contrast, palladized nanosized ZVI (Pd/nFe) rapidly dechlorinates PCDDs, including the mono- to tetra-chlorinated congeners. The rate of 1,2,3,4-tetrachloro dibenzo-p-dioxin (1,2,3,4-TeCDD) degradation using Pd/nFe was about 3 orders of magnitude faster than 1,23,4-TeCDD degradation using unpalladized ZVI. The distribution of products obtained from dechlorination of 1,2,3,4-TeCDD suggests that palladization shifts the pathways of contaminant degradation toward a greater role of H atom transfer rather than electron transfer.     

Efficient decomposition of environmentally persistent perfluorooctanesulfonate and related fluorochemicals using zerovalent iron in subcritical water

Decomposition of perfluorooctanesulfonate (PFOS) and related chemicals in subcritical water was investigated. Although PFOS demonstrated little reactivity in pure subcritical water, addition of zerovalent metals to the reaction system enhanced the PFOS decomposition to form F-ions, with an increasing order of activity of no metal approximately equal Al < Cu < Zn < Fe. Use of iron led to the most efficient PFOS decomposition: When iron powder was added to an aqueous solution of PFOS (93-372 microM) and the mixture was heated at 350 degrees C for 6 h, PFOS concentration in the reaction solution fell below 2.2 microM (detection limit of HPLC with conductometric detection), with formation of F-ions with yields [i.e., (moles of F- formed)/(moles of fluorine content in initial PFOS) x 100] of 46.2-51.4% and without any formation of perfluorocarboxylic acids. A small amount of CHF3 was detected in the gas phase with a yield [i.e., (moles of CHF3)/(moles of carbon content in initial PFOS) x 100] of 0.7%, after the reaction of PFOS (372 microM) with iron at 350 degree C for 6 h. Spectroscopic measurements indicated that PFOS in water markedly adsorbed on the iron surface even at room temperature, and the adsorbed fluorinated species on the iron surface decomposed with rising temperature, with prominent release of F- ions to the solution phase above 250 degrees C. This method was also effective in decomposing other perfluoroalkylsulfonates bearing shorter chain (C2-C6) perfluoroalkyl groups and was successfully applied to the decomposition of PFOS contained in an antireflective coating agent used in semiconductor manufacturing.     

Kinetics of soluble chromium removal from contaminated water by zerovalent iron media: corrosion inhibition and passive oxide effects

Permeable reactive barriers containing zerovalent iron are being increasingly employed for in situ remediation of groundwater contaminated with redox active metals and chlorinated organic compounds. This research investigated the effect of chromate concentration on its removal from solution by zerovalent iron. Removal rates of aqueous Cr(VI) by iron wires were measured in batch experiments for initial chromium concentrations ranging from 100 to 10 000 microg/L. Chromate removal was also measured in columns packed with zerovalent iron filings over this same concentration range. Electrochemical measurements were made to determine the free corrosion potential and corrosion rate of the iron reactants. In both the batch and column reactors, absolute rates of chromium removal declined with increasing chromate concentration. Corrosion current measurements indicated that the rate of iron corrosion decreased with increasing Cr(VI) concentrations between 0 and 5000 microg/L. At a Cr(VI) concentration of 10 000 microg/L, Tafel polarization diagrams showed that chromium removal was affected by its diffusion rate through a passivating oxide film and by the ability of iron to release Fe2+ at anodic sites. In contrast, water reduction was not mass transfer limited, but chromium did decrease the exchange current for the hydrogen evolution reaction. Even at the most passivating concentration of 10 000 microng/L, effluent Cr(VI) concentrations in the column reactors reached a steady state, indicating that passivation had also reached a steady state. Although chromate contributes to iron surface passivation, the removal rates are still sufficiently fast for in situ iron barriers to be effective for Cr(VI) removal at most environmentally relevant concentrations.     

Reduction of octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine by zerovalent iron: product distribution

RDX (hexahydro-1,3,5-trinitro-1,3,5-triazine) and HMX (octahydro-1,3,5,7-tetranitro-1,3,5,7-tetrazocine) are cyclic nitramines ((CH2NNO2)n; n = 3 or 4, respectively) widely used as energetic chemicals. Their extensive use led to wide environmental contamination. In contrast to RDX, HMX tends to accumulate in soils due to its unique recalcitrance. In the present study, we investigated the potential of zerovalent iron (ZVI) to transform HMX under anoxic conditions. HMX underwent a rapid transformation when added in well-mixed anoxic ZVI-H2O batch systems to ultimately produce formaldehyde (HCHO), ammonium (NH4+), hydrazine (NH2NH2), and nitrous oxide (N2O). Time course experiments showed that the mechanism of HMX transformation occurred through at least two initial reactions. One reaction involved the sequential reduction of N-NO2 groups to the five nitroso products (1NO-HMX, cis-2NO-HMX, trans-2NO-HMX, 3NO-HMX, and 4NO-HMX). Another implied ring cleavage from either HMX or 1NO-HMX as demonstrated by the observation of methylenedinitramine (NH(NO2)CH2NH(NO2)) and another intermediate that was tentatively identified as (NH(NO2)CH2N(NO)CH2NH-(NO2)) or its isomer (NH(NO)CH2N(NO2)CH2NH(NO2)). This is the first study that demonstrates transformation of HMX by ZVI to significant amounts of NH2NH2 and HCHO. Both toxic products seemed to persist under reductive conditions, thereby suggesting that the ultimate fate of these chemicals, particularly hydrazine, should be understood prior to using zerovalent iron to remediate cyclic nitramines.     

Arsenic removal from Bangladesh tube well water with filter columns containing zerovalent iron filings and sand

Arsenic removal is often challenging due to high As(III), phosphate, and silicate concentrations and low natural iron concentrations. Application of zerovalent iron is promising, as metallic iron is widely available. However, removal mechanisms remained unclear and currently used removal units with iron have not been tested systematically, partly due to their large size and long operation time. This study investigated smaller filter columns with 3-4 filters, each containing 2.5 g of iron filings and 100-150 g of sand. At a flow rate of 1 L/h, these columns were able to treat 75-90 L of well water with 440 microg/L As, 1.8 mg/L P, 4.7 mg/L Fe, 19 mg/L Si, and 6 mg/L dissolved organic carbon (DOC) to below 50 microg/L As(tot), without addition of an oxidant. As(III) was oxidized in parallel to oxidation of corrosion-released Fe(II) by dissolved oxygen and sorbed on the forming hydrous ferric oxides (HFO). The open filter columns prevented anoxic conditions. DOC did not appear to interfere with arsenic removal. Manganese was reduced after a slight initial increase from 0.3 mg/L to below 0.1 mg/L. About 100 mg of Fe(0)/L of water was required, 3-5 times less than that for larger units with sand and iron turnings.     

Removal of arsenic from groundwater by zerovalent iron and the role of sulfide

Several recent investigations have shown encouraging potential for the removal of arsenic (As) from groundwater by granular zerovalent iron (Fe0). In contrast to previous studies conducted, we have investigated the applicability of this method and the nature of As bonding under conditions with dissolved sulfide. Three column tests were performed over the period of 1 year using solutions with either As(V) or As(II) (2-200 mg/L) in the input solution. Arsenic outflow concentrations decreased from initially 30-100 microg/L to concentrations of below 1 microg/L with time. XANES (X-ray absorptions near edge structure) and EXAFS (expanded X-ray absorption fine structure) spectra indicated that As in the solid phase is not only directly coordinated with oxygen, as is the case in adsorbed or coprecipitated arsenite and arsenate. Samples with high sulfur content showed additional bonding, for which Fourier transformations of EXAFS data exhibited a peak between 2.2 and 2.4 A. This bonding most likely originated from the direct coordination of sulfur or iron with As, which was incorporated in iron sulfides orfrom adsorbed thioarsenites. The formation of this sulfide bonding supports the removal of As by Fe0 because sulfide production by microbial sulfate reduction is ubiquitous in permeable reactive barriers composed of Fe0.     

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.     

Effect of precipitation on low frequency electrical properties of zerovalent iron columns

We conducted column studies to investigate the application of a noninvasive electrical method to monitor precipitation in Fe0 columns using (a) Na2SO4 (0.01 M, dissolved oxygen (DO) = 8.8 ppm), and (b) Na2CO3 (0.01 M, DO = 2.3 ppm) solutions. An increase in complex conductivity terms (maximum 40% in sulfate column and 23% in carbonate column) occurred over 25 days. Scanning electron microscopy (SEM) identified mineral surface alteration, with greater changes in the high DO sulfate column relative to the low DO carbonate column. X-ray diffractometry (XRD) identified reduced amounts of hematite/maghemite in both columns, precipitation of goethite/akaganeite in the sulfate column, and precipitation of siderite in the carbonate column. Nitrogen adsorption measurements showed increases in specific surface area of iron minerals (27.5% for sulfate column and 8.2% for carbonate column). As variations in electrolytic conductivity and porosity were minimal, electrical 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. Our results show that electrical measurements are a proxy indicator of Fe0 surface alteration.     

Uranium precipitation in a permeable reactive barrier by progressive irreversible dissolution of zerovalent iron

A permeable reactive barrier (PRB) containing zerovalent iron [Fe(O)] was installed at a former uranium milling site in Monticello, UT. A large-scale column experiment was conducted at the site to test the feasibility of Fe(O) to treat U prior to installing the PRB. Effluents from the field column experiment had pH values near 7.34, moderate decreases in C(IV) and Ca concentrations, and an elevated Fe concentration (27.1 mg/L). In contrast, groundwater exiting the PRB had a pH value of 9.82, decreases in C(IV) and Ca concentrations, and a low concentration of Fe (0.17 mg/L). A geochemical model was used to explain the chemical changes that occurred in both the field column experiment and the PRB. The model simulated the systems by the progressive irreversible dissolution of Fe(O). Modeling results indicated that a longer residence time in the PRB compared with the shorter residence time in the column contributed to the disparate effluent qualities. Prior to modeling, a controlled laboratory column experiment was conducted to help evaluate the dominant chemical mechanisms by which Fe(O) removes U from aqueous solutions. Results of the laboratory column experiment indicated that only a small amount of U could be adsorbed to ferric minerals, and, therefore, this mechanism was not considered in the model.