Reactivity Of Nanoscale Zero-valent Iron Research Articles

Impact of the morphology and reactivity of nanoscale zero-valent iron (NZVI) on dechlorinating bacteria

Nanoscale zero-valent iron (NZVI) is increasingly used for reducing chlorinated organic contaminants in soil or groundwater. However, little is known about what impact the particles will have on the biochemical processes and the indigenous microbial communities. Nanoiron reactivity is affected by the structure and morphology of nanoparticles that complicates the applicability in bioremediation. In this study, the effect of precursors (ferrous sulfate and ferric chloride) and reducing agents (sodium dithionite and sodium borohydride) on the morphology and the reactivity of NZVIs was investigated. We also studied the impact of differently synthesized NZVIs on microbial community, which take part in reductive dechlorination. We demonstrated that both the applied iron precursor and the reducing agent had influence on the structure of the nanoparticles. Spherical nanoparticles with higher Fe0 content (>90%) was observed by using sodium borohydride as reducing agent, while application of sodium dithionite as reducing agent resulted nanostructures with lower Fe0 content (between 68,7 and 85,5%). To determine the influence of differently synthesized NZVIs on cell viability anaerobic enriched microcosm were used. NVZI was used in 0.1 g/L concentration in all batch experiments. Relative amount of Dehalococcoides, sulfate reducers (SRBs) and methanogens were measured by quantitative PCR. We found that the relative amount of Dehalococcoides slowly decreased in all experiments independently from the precursor and reducing agent, whereas the total amount of microbes increased. The only clear distinction was in relative amount of sulfate reducers which were higher in the presence of NZVIs synthesized from sodium dithionite.

Influence of fulvic acid on the colloidal stability and reactivity of nanoscale zero-valent iron

This study investigated the effect of fulvic acid (FA) on the colloidal stability and reactivity of nano zero-valent iron (nZVI) at pH 5, 7 and 9. The sedimentation behavior of nZVI differed at different pH. A biphasic model was used to describe the two time-dependent settling processes (i.e., a rapid settling followed by a slower settling) and the settling rates were calculated. Generally, the settling of nZVI was more significant at the point of zero charge (pHpzc), which could be varied in the presence of FA due to the adsorption of FA on the nZVI surface. More FA was adsorbed on the nZVI surface at pH 5–7 than pH 9, resulting in the varying sedimentation behavior of nZVI via influencing the electrostatic repulsion among particles. Moreover, it was found that there was a tradeoff between the stabilization and the reactivity of nZVI as affected by the presence of FA. When FA concentration was at a low level, the adsorption of FA on the nZVI surface could enhance the particle stabilization, and thus facilitating the Cr(VI) reduction by providing more available surface sites. However, when the FA concentrations were too high to occupy the active surface sites of nZVI, the Cr(VI) reduction could be decreased even though the FA enhanced the dispersion of nZVI particles. At pH 9, the FA improved the Cr(VI) reduction by nZVI. Given the adsorption of FA on the nZVI surface was insignificant and its effect on the settling behavior of nZVI particles was minimal, it was proposed that the FA formed soluble complexes with the produced Fe(III)/Cr(III) ions, and thus reducing the degree of passivation on the nZVI surface and facilitating the Cr(VI) reduction.

Enhanced reactivity of nanoscale zero-valent iron prepared by a rotating packed bed with blade packings

Nanoscale zero-valent iron (nZVI) was prepared by continuously pumping aqueous FeCl2·4H2O (0.1mol/L) and NaBH4 (0.2mol/L) into a rotating packed bed (RPB) with blade packings. A rotational speed of 1400rpm, liquid flow rates of 0.6L/min, and a temperature of 21°C were used. nZVI that was prepared in this way had a mean grain size of 11.5nm and a BET surface area of 17.1m2/g. The reactivity of the thus prepared nZVI was measured using the degradation of Reactive Red 2 (RR2) in the presence of dissolved oxygen. At pH 4 and 30°C with an nZVI dosage of 0.30g/L, the prepared nZVI degraded approximately 92% of the RR2 in 5min; this efficiency of degradation greatly exceeded that obtained using nZVI that was purchased from Centron Biochemistry Technology (CBT).

Reactivity of Nanoscale Zero-Valent Iron in Unbuffered Systems: Effect of pH and Fe(II) Dissolution.

While most published studies used buffers to maintain the pH, there is limited knowledge regarding the reactivity of nanoscale zerovalent iron (NZVI) in poorly buffered pH systems to date. In this work, the effect of pH and Fe(II) dissolution on the reactivity of NZVI was investigated during the reduction of 4-nitrophenol (4-NP) in unbuffered pH systems. The reduction rate increased exponentially with respect to the NZVI concentration, and the ratio of dissolved Fe(II)/initial NZVI was related proportionally to the initial pH values, suggesting that lower pH (6-7) with low NZVI loading may slow the 4-NP reduction through acceleration of the dissolution of NZVI particles. Additional experiments using buffered pH systems confirmed that high pH values (8-9) can preserve the NZVI particles against dissolution, thereby enhancing the reduction kinetics of 4-NP. Furthermore, reduction tests using ferrous ion in suspensions of magnetite and maghemite showed that surface-bound Fe(II) on oxide coatings can play an important role in enhancing 4-NP reduction by NZVI at pH 8. These unexpected results highlight the importance of pH and Fe(II) dissolution when NZVI technology is applied to poorly buffered systems, particularly at a low amount of NZVI (i.e., <0.075 g/L).

Effect of Fe loading quantity on reduction reactivity of nano zero-valent iron supported on chelating resin

In this study, nanoscale zero-valent iron (NZVI) were immobilized within a chelating resin (DOW 3N). To investigate the effect of Fe loading on NZVI reactivity, three NZVI-resin composites with different Fe loading were obtained by preparing Fe(III) solution in 0, 30 and 70% (v/v) ethanol aqueous, respectively; the bromate was used as a model contaminant. TEM reveals that increasing the Fe loading resulted in much larger size and poor dispersion of nanoscale iron particles. The results indicated that the removal efficiency of bromate and the rate constant (Kobs) were decreased with increasing the Fe loading. For the NZVI-resin composite with lower Fe loading, the removal efficiency of bromate declined more significantly with the increase of DO concentrations. Under acidic conditions, decreasing the pH value had the most significant influence on NZVIR3 with highest Fe loading for bromate removal; however, under alkaline conditions, the most significant influence of pH was on NZVI-R1 with lowest Fe loading. The effects of co-existing anions NO3–, PO43– and HCO3– were also investigated. All of the co-existing anions showed the inhibition to bromate reduction.

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

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.

Enhanced removal of uranium(VI) by nanoscale zerovalent iron supported on Na-bentonite and an investigation of mechanism.

The reductive removal of U(VI) by nanoscale zerovalent iron (NZVI) was enhanced by using Na(+)-saturated bentonite (Na-bent) as the support, and the mechanism for the enhanced removal were investigated comprehensively. Under the same experimental conditions, NZVI supported on the negatively charged Na-bent showed much higher removal efficiency (99.2%) of cationic U(VI) than either bare NZVI (48.3%) or NZVI supported on the positively charged bentonite (Al-bent) did. Subsequent experimental investigations revealed the unique roles of bentonite on enhancing the reactivity and reusability of NZVI. First, Na-bent can buffer the pH in reaction media, besides preventing NZVI from aggregation. Second, Na-bent promoted the mass transfer of U(VI) from solution to NZVI surface, leading to the enhanced removal efficiency. Third, the bentonite may transfer some insoluble reduction products away from the iron surface according to X-ray absorption fine structure (XAFS) study. Finally, Na-bent as the adsorbent to Fe(II) makes it more reactive with U(VI), which enhanced stoichiometrically the reduction capacity of NZVI besides accelerating the reaction rate.

Influence of Riboflavin on Nanoscale Zero-Valent Iron Reactivity during the Degradation of Carbon Tetrachloride

Experiments were conducted to investigate the effect of riboflavin on the reactivity of nanoscale zerovalent iron (NZVI) during three reaction cycles of carbon tetrachloride (CT) degradation. The degradation kinetics of CT by NZVI without riboflavin (0.556 ± 0.044 h(-1)) was 1.5 times higher than that with riboflavin (0.370 ± 0.012 h(-1)) in the first cycle. Riboflavin was rapidly reduced (65.0 ± 7.0 h(-1)) by NZVI during CT degradation, resulting in the slow degradation kinetics of CT in the first cycle due to competition for electrons from NZVI between riboflavin and CT. These results indicate that riboflavin is not effective as an electron shuttle for reduction of CT by NZVI. On the other hand, the degradation kinetics of CT by NZVI without riboflavin decreased to 0.122 ± 0.033 h(-1) in the third cycle, while that with riboflavin was significantly enhanced (0.663 ± 0.005 h(-1)). The results from X-ray analyses and transmission electron microscopy suggest that the decline in reactivity of NZVI without riboflavin in the third cycle resulted from continuous Fe(0) oxidation to iron oxides on the NZVI surface. In contrast, riboflavin enhanced the reactivity of NZVI by reductive dissolution of passive iron oxides on NZVI surface by reduced riboflavin. The experimental results suggest that riboflavin can play a pivotal role in the prolongation of NZVI reactivity in long-term in situ and ex situ applications of NZVI.

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

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; HCO3−) 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.

Enhanced reduction of chlorophenols by nanoscale zerovalent iron supported on organobentonite

The reactivity of nanoscale zerovalent iron (NZVI) on removing chlorophenols (2-chlorophenol, 2,4-dichlorophenol, 2,4,6-trichlorophenol and pentachlorophenol) was remarkably enhanced by using a hydrophobic support of organobentonite (CTMA-Bent), namely the bentonite modified with organic cetyltrimethylammonium (CTMA) cations. The complete dechlorination of chlorophenols and total conversion into phenol using this novel NZVI/CTMA-Bent combination was observed in batch experiments. The kinetic studies suggested that the reduction of chlorophenols by NZVI was accelerated due to the enhanced adsorption onto CTMA-Bent, which facilitated the mass transfer of chlorophenols from aqueous to iron surface. The enhanced reduction rate by NZVI/CTMA-Bent was positively related to the hydrophobicity of chlorophenols, and an increasing linear relationship was obtained between the relative enhancement on reaction rate constants (k2/k1) and logKow values of chlorophenols. XPS results suggested there were fewer precipitates of ferric (hydro)xides formed on the surface of NZVI/CTMA-Bent, which may also lead to the improved reactivity and repetitive usability of NZVI/CTMA-Bent on removing chlorophenols.

Humic acid characteristics and effects on the reactivity of nano-scale zero-valent iron particles during nitrate reduction

ABSTRACT Humic acid (HA) comprises a significant fraction of natural organic matter (NOM), greatly influencing the performance of water and wastewater treatment processes. HA is expected to significantly affect the reactivity of nano-scale zero-valent iron (NZVI), which is receiving increasing attention due to its high reactivity. The effects of HA on nitrate reduction by NZVI were investigated to evaluate the potential of NZVI in practical applications. HA was characterized to identify the mechanism whereby HA affects. Nitrate reduction was enhanced at low HA concentration, but inhibited as HA concentration increased. HA decreased to reach a plateau and considerable amount of Fe3+ was detected when HA was present in dissolved phase. The increase in the degree of condensation of HA was verified by UV–vis spectroscopy, fluorescence spectroscopy, and size exclusion chromatography. Fourier transform infrared spectra confirmed that the Fe3+–HA complexes were formed in both the dissolved and solid fractions, without coexisting metal ions. The HA aggregation on NZVI and discrete HA macroaggregates were observed by transmission electron microscopy. The results suggest that HA induces complex effects on NZVI reactivity by improving iron dissolution, inhibiting readsorption of released iron, enhancing electron transfer, and inhibiting nitrate mass transfer via forming HA accumulation. It indicates that the clogging by aggregated NOM should be considered when NZVI is used for groundwater treatment or in combination with porous materials.

Influence of Anionic Cosolutes and pH on Nanoscale Zerovalent Iron Longevity: Time Scales and Mechanisms of Reactivity Loss toward 1,1,1,2-Tetrachloroethane and Cr(VI)

Nanoscale zerovalent iron (NZVI) was aged over 30 days in suspension (2 g/L) with different anions (chloride, perchlorate, sulfate, carbonate, nitrate), anion concentrations (5, 25, 100 mN), and pH (7, 8). During aging, suspension samples were reacted periodically with 1,1,1,2-tetrachloroethane (1,1,1,2-TeCA) and Cr(VI) to determine the time scales and primary mode of NZVI reactivity loss. Rate constants for 1,1,1,2-TeCA reduction in Cl(-), SO(4)(2-), and ClO(4)(-) suspensions decreased by 95% over 1 month but were generally equivalent to one another, invariant of concentration and independent of pH. In contrast, longevity toward 1,1,1,2-TeCA depended upon NO(3)(-) and HCO(3)(-) concentration, with complete reactivity loss over 1 and 14 days, respectively, in 25 mN suspensions. X-ray diffraction suggests that reactivity loss toward 1,1,1,2-TeCA in most systems results from Fe(0) conversion into magnetite, whereas iron carbonate hydroxide formation limits reactivity in HCO(3)(-) suspensions. Markedly different trends in Cr(VI) removal capacity (mg Cr/g NZVI) were observed during aging, typically exhibiting greater longevity and a pronounced pH-dependence. Notably, a strong linear correlation exists between Cr(VI) removal capacities and rates of Fe(II) production measured in the absence of Cr(VI). While Fe(0) availability dictates longevity toward 1,1,1,2-TeCA, this correlation suggests surface-associated Fe(II) species are primarily responsible for Cr(VI) reduction.

Electrokinetic-enhanced nanoscale iron reactive barrier of trichloroethylene solubilized by Triton X-100 from groundwater

The objective of this study is to investigate the performances of permeable reactive barrier (PRB) packed with nanoscale zero-valent iron (NZVI) particles enhanced by surfactant and electrokinetics (EK) on trichloroethylene (TCE) degradation. The optimal operation parameters obtained from the tests conducted in a lab-scale sandbox were the potential gradient of 1Vcm−1, NZVI loading of 5g, and PRB located behind the anode, and were adopted for the following transport and degradation experiments conducted in the bench-scale sandbox. Chlorinated byproducts were not detected during the lab-scale sandbox tests, i.e. TCE was completely dechlorinated by NZVI particles in the reactive barrier. The results of bench-scale sandbox tests revealed that TX100 surfactant raised the mobility and solubility of TCE in aquifer that increased its availability for further dechlorination of NZVI. Advection and dispersion were the main factors on reduction of TX100 while adsorption of sand had higher influences on the decrease of TCE. The concentrations of TCE in the lower layer are higher than those in the upper layer owing to its dense non-aqueous phase liquid (DNAPL) properties. EK can promote the reactivity of NZVI by releasing H+ near anode. H+ not only participates in TCE dechlorination reaction but also washes away the precipitates on surface of NZVI to maintain its activity. Fe2+ and Cl− were continuously produced accompanying with TCE degradation showing that TCE was dechlorinated by NZVI particles. This study shows that NZVI coupling with EK can promote the degradation of TCE in groundwater.

Adsorption and dechlorination of 2,4-dichlorophenol (2,4-DCP) on a multi-functional organo-smectite templated zero-valent iron composite

Controlling the reactivity of nano-scale zero-valent iron (nZVI) remains a challenge for its practical application. In the present study, smectite-templated nZVI is hydrophobized by adding N,N,N-trimethyl-1-dodecanaminium salt (DTA+) to yield organo-smectite-ZVI. The obtained material was characterized by XRD, TEM and FTIR. Its reactivity was evaluated for the aqueous removal of 2,4-DCP. Results show that (i) nanosized ZVI clusters of <5nm are intercalated into the clay interlayers; (ii) hydrophobization of smectite surfaces occurs after binding of DTA+ to the clay minerals; (iii) aqueous 2,4-DCP could be rapidly accumulated in the vicinity of the solid phase; (iv) accumulated 2,4-DCP is then gradually dechlorinated. This demonstrates that hydrophobic conditions in clay interlayer facilitate the 2,4-DCP adsorption. In a 2,4-DCP successive addition systems, dechlorination can be maintained even after five cycles for organo-smectite-ZVI, but just two cycles for smectite-ZVI. This indicates that the hydrophobization of smectite-ZVI could significantly sustain its reactivity and inhibit the rapid consumption of ZVI in the Fe0/H2O system. This statement is supported by XPS analysis. Furthermore, organo-smectite-ZVI provides strong adsorptive affinity to 2,4-DCP and its reaction products. This is beneficial for the long-term stability of removed contaminants.

Removal of trichloroethylene DNAPL trapped in porous media using nanoscale zerovalent iron and bimetallic nanoparticles: Direct observation and quantification

Direct trichloroethylene (TCE) dense non-aqueous phase liquid (DNAPL) removal inside pore areas using nanoscale zerovalent iron (NZVI) and bimetallic nanoparticles were first investigated in a water-saturated porous glass micromodel. Effects of nitrate, aqueous ethanol co-solvent, humic substance, and elapsed time on TCE DNAPL removal using NZVI were studied by direct visualization. The removal efficiency was then quantified by directly measuring the remaining TCE DNAPL blobs area using an image analyzer. As ethanol content of co-solvent increased, TCE DNAPL removal by NZVI was also increased implying sequential TCE DNAPL removal mechanisms: as dissolved TCE was degraded by NZVI, TCE dissolution from TCE blobs would be then facilitated and the TCE blob areas would be eventually reduced. The presence of nitrate and humic substance hindered the NZVI reactivity for the TCE DNAPL removal. In contrast, the TCE DNAPL removal efficiency was enhanced using bimetallic nanoparticles in a short-term reaction by generating atomic hydrogen for catalytic hydro-dechlorination. However, all TCE DNAPL removal efficiencies reached the same level after long-term reaction using both NZVI and bimetallic nanoparticles. Direct TCE DNAPL observation clearly implied that TCE blobs existed for long time even though all TCE blobs were fully exposed to NZVI and bimetallic nanoparticles.

Enhanced removal of pentachlorophenol by a novel composite: Nanoscale zero valent iron immobilized on organobentonite

Nanoscale zero valent iron (NZVI) was immobilized on the organobentonite (CTMA-bent), so as to enhance the reactivity of NZVI and prevent its aggregation. This novel composite (NZVI/CTMA-Bent) was characterized by transmission electron microscope and X-ray diffraction. Good dispersion of NZVI particles on the bentonite was observed. Its performance on removing pentachlorophenol (PCP) was investigated by batch experiments. Results showed NZVI/CTMA-Bent could rapidly and completely dechlorinate PCP to phenol with an efficiency of 96.2%. It was higher than the sum (54.5%) of reduction by NZVI (31.5%) and adsorption by CTMA-Bent (23.0%) separately. The kinetic studies indicated the removal rate of PCP was positively related to the adsorption. We proposed that the adsorption of PCP by CTMA-Bent enhanced the mass transfer of PCP from aqueous to iron surface. Besides, NZVI/CTMA-Bent exhibited good stability and reusability, and CTMA-Bent could also reduce the amount of iron ions released into the solution.

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

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

Use of Dithionite to Extend the Reactive Lifetime of Nanoscale Zero-Valent Iron Treatment Systems

Nanoscale zero-valent iron (NZVI) represents a promising approach for source zone control, but concerns over its reactive lifetime might limit application. Here, we demonstrate that dithionite (S₂O₄²⁻), a reducing agent for in situ redox manipulation, can restore the reducing capacity of passivated NZVI. Slurries of NZVI were aged in the presence (3 days) and absence (60 days) of dissolved oxygen over a range of pH values (6-8). Upon loss of reactivity toward model pollutants{1,1,1,2-tetrachloroethane, hexavalent chromium [Cr(VI)], nitrobenzene}, aged suspensions were reacted with dithionite, and the composition and reactivity of the dithionite-treated materials were determined. NZVI aging products generally depended on pH and the presence of oxygen, whereas the amount of dithionite influenced the nature and reducing capacity of products generated from reaction with aged NZVI suspensions. Notably, air oxidation at pH ≥ 8 quickly exhausted NZVI reactivity despite preservation of significant Fe(0) in the particle core. Under these conditions, formation of a passive surface layer hindered the complete transformation of NZVI particles into iron(III) oxides, which occurred at lower pH. Reduction of this passive layer by low dithionite concentrations( 1 g/g of NZVI) restored suspension reactivity to levels equal to, and occasionally greater than, that of unaged NZVI. Multiple dithionite additions further improved pollutant removal, allowing at least a 15-fold increase in Cr(VI) removal [∼300 mg of Cr(VI)/g of NZVI] relative to that of as-received NZVI [∼20 mg of Cr(VI)/g of NZVI].

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

A 200m2 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.

Evaluation of nanoscale zerovalent iron particles for trichloroethene degradation in clayey soils

The longevity and reactivity of nanoscale zerovalent iron (nZVI) and palladized bimetallic particles (BNP) were evaluated in batch and column experiments for remediation of a trichloroethene (TCE)-contaminated plume within a clayey soil from Oak Ridge Reservation (ORR). Comparative studies assessing the viability of BNP and nZVI confirmed that particle behavior is severely affected by clay sediments. Surface morphology and composition analyses using SEM and SEM–energy-dispersive spectroscopy spectrum revealed particle agglomeration through the formation of clay–iron aggregates of greater mass during the early phase of the experiment. Batch study results suggest that TCE degradation in ORR clayey soil follows a pseudo-first-order kinetic model exhibiting reaction rate constants ( k) of 0.05–0.24 day − 1 at varied iron-to-soil ratios. Despite high reactivity in water, BNP were less effective in the site-derived clay sediment with calculated TCE removal efficiencies of 98.7% and 19.59%, respectively. A column experiment was conducted to investigate particle longevity and indicator parameters of the TCE degradation process under flow conditions. It revealed that the TCE removal efficiency gradually declined over the course of the experiment from 86–93% to 51–52%, correlating to a progressive increase in oxidation–reduction potential (ORP) from − 485 to − 250 mV and pH drop from 8.2–8.6 to 7.4–7.5. The rate of nZVI deactivation reaction was found to be a first order with a k d value of 0.0058 day − 1 . SEM images of residual nZVI revealed heavily agglomerated particles. However, despite widespread oxidation and agglomeration, particles managed to maintain some capacity for oxidation. A quantitative analysis of nZVI deactivation has the potential of predicting nZVI longevity in order to improve the design strategy of TCE remediation.