Effects of pH on dechlorination of trichloroethylene by zero-valent iron

The surface normalized reaction rate constants (k(sa)) of trichloroethylene (TCE) and zero-valent iron (ZVI) were quantified in batch reactors at pH values between 1.7 and 10. The k(sa) of TCE linearly decreased from 0.044 to 0.009l/hm(2) between pH 3.8 and 8.0, whereas the k(sa) at pH 1.7 was more than an order higher than that at pH 3.8. The degradation of TCE was not observed at pH values of 9 and 10. The k(sa) of iron corrosion linearly decreased from 0.092 to 0.018l/hm(2) between pH 4.9 and 9.8, whereas it is significantly higher at pH 1.7 and 3.8. The k(sa) of TCE was 30-300 times higher than those reported in literature. The difference can be attributed to the pH effects and precipitation of iron hydroxide. The k(sa) of TCE degradation and iron corrosion at a head space of 6 and 10ml were about twice of those at zero head space. The effect was attributed to the formation of hydrogen bubbles on ZVI, which hindered the transport the TCE between the solution and reaction sites on ZVI. The optimal TCE degradation rate was achieved at a pH of 4.9. This suggests that lowering solution pH might not expedite the degradation rate of TCE by ZVI as it also caused faster disappearance of ZVI, and hence decreased the ZVI surface concentration.     

Removal of arsenic from water by zero-valent iron

Batch and column experiments were conducted to investigate the effect of dissolved oxygen (DO) and pH on arsenic removal with zero-valent iron [Fe(0)]. Arsenic removal was dramatically affected by the DO content and the pH of the solution. Under oxic conditions, arsenate [As(V)] removal by Fe(0) filings was faster than arsenite [As(III)]. Greater than 99.8% of the As(V) was removed whereas 82.6% of the As(III) was removed at pH 6 after 9h of mixing. When the solution was purged with nitrogen gas to remove DO, less than 10% of the As(III) and As(V) was removed. High DO content and low solution pH also increased the rate of iron corrosion. The removal of arsenic by Fe(0) was attributed to adsorption by iron hydroxides generated from the oxic corrosion of Fe(0). The column results indicated that a filtration system consisting of an iron column and a sand filter could be used for treatment of arsenic in drinking water.     

Degradation of perchloroethylene in cosolvent solutions by zero-valent iron

Remediation of sites contaminated by chlorinated organic compounds is a significant priority in the environmental field. Subsequently, the addition of cosolvent solutions for in situ flushing of contaminated source zones has been successfully field tested. However, the treatment of effluent fluids in such cleanup efforts is an often overlooked component of this technology implementation. The purpose of this research was to evaluate the effectiveness of zero-valent iron (Fe(0)) in treating perchloroethylene (PCE) in an aqueous solution, and how the presence of a cosolvent (ethanol) and modification of the iron surface altered dechlorination. The modified iron surfaces included in this study were nickel-plated iron, acid-treated iron, and untreated iron surfaces. PCE dechlorination in the presence of each of the iron surfaces displayed pseudo first-order kinetics. The highest degradation rate of PCE occurred on the nickel-plated iron surface, 5.83 x 10(-3)h(-1), followed by the acid-treated iron, 4.92 x 10(-3)h(-1), and the untreated iron, 3.34 x 10(-3)h(-1). Dechlorination on each of the surfaces decreased with increasing cosolvent fractions. It was shown that as cosolvent fractions increased, PCE adsorption decreased and resulted in a concomitant decrease in PCE degradation rates.     

Enhanced reduction of nitrate by zero-valent iron at elevated temperatures

Kinetics of nitrate reduction by zero-valent iron at elevated temperatures was studied through batch and column experiments. It was hypothesized that under increased solution temperatures, the zero-valent iron may accelerate the reduction of nitrate by overcoming the activation energy barrier to nitrate reduction. The results of the batch experiment showed the synergistic effects of elevated temperature (75 degrees C) and a buffered condition (pH 7.4 with 0.1 M HEPES) to enhance the rate of nitrate reduction by zero-valent iron from 0.072+/-0.006 h(-1) ((0.35+/-0.03) x 10(-4) L m(-2) h(-1)) at room temperature to 1.39+/-0.23 h(-1) ((1.03+/-0.07) x 10(-3) L m(-2) h(-1)). Complete nitrate removal was obtained in a Fe(0) column after 30 min under both buffered and unbuffered conditions at 75 degrees C. These results indicate that a temperature increase could overcome the energy barrier. We suggest that an iron reduction process at moderately elevated temperature (50-75 degrees C) may be a suitable method for removing nitrate from industrial discharges.     

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.     

Effects of ferrous ions on the reductive dechlorination of trichloroethylene by zero-valent iron

The surface characteristics of zero-valent iron (ZVI) and the efficiency of reductive dechlorination of trichloroethylene (TCE) in the presence of ferrous ions were studied. The experimental results indicated that the acid-washing of a metallic iron sample enhanced the efficiency of TCE degradation by ZVI. This occurred because acid-washing changed the conformation of oxides on the surface of iron from maghemite (gamma-Fe(2)O(3)) to the more hydrated goethite (alpha-FeOOH), as was confirmed by XPS analysis. However, when ferrous ions were simultaneous with TCE in water, the TCE degradation rate decreased as the concentration of ferrous ion increased. This was due to the formation of passive precipitates of ferrous hydroxide, including maghemite and magnetite (Fe(3)O(4)), that coated on the surface of acid-washed ZVI, which as a result inhibited the electron transfer and catalytic hydrogenation mechanisms. On the other hand, in an Fe(0)-TCE system without the acid-washing pretreatment of ZVI, ferrous ions were adsorbed into the maghemite lattice which was then converted to semiconductive magnetite. Thus, the electrons were transferred from the iron surface and passed through the precipitates, allowing for the reductive dechlorination of TCE.     

Advanced treatment of coking wastewater by coagulation and zero-valent iron processes

Advanced treatment of coking wastewater was investigated experimentally with coagulation and zero-valent iron (ZVI) processes. Particular attention was paid to the effect of dosage and pH on the removal of chemical oxygen demand (COD) in the two processes. The results showed that ZVI was more effective than coagulation for advanced treatment of coking wastewater. The jar tests revealed that maximal COD removal efficiency of 27.5-31.8% could be achieved under the optimal condition of coagulation, i.e. 400mg/L of Fe(2)(SO(4))3 as coagulant at pH 3.0-5.0. On the other hand, the COD removal efficiency could be up to 43.6% under the idealized condition of ZVI upon 10 g/L active carbon and 30 g/L iron being dosed at pH 4.0. The mechanisms for COD removal in ZVI were dominated by coagulation, precipitation and oxidation-reduction. ZVI would also enhance the biodegradability of effluent by increasing BOD5/COD from 0.07 to 0.53. Moreover, some ester compounds could be produced in the reaction. Although ZVI was found more efficient than coagulation in eliminating low molecular weight (<2000 Da) compounds in the wastewater, there were still a few residual contaminants which could hardly be eliminated by either of the process.     

Study on treatment of coking wastewater by biofilm reactors combined with zero-valent iron process

Experiments were conducted to investigate the behavior of the integrated system with biofilm reactors and zero-valent iron (ZVI) process for coking wastewater treatment. Particular attention was paid to the performance of the integrated system for removal of organic and inorganic nitrogen compounds. Maximal removal efficiencies of chemical oxygen demand (COD), ammonia nitrogen (NH(3)-N) and total inorganic nitrogen (TIN) were up to 96.1, 99.2 and 92.3%, respectively. Moreover, it was found that some phenolic compounds were effectively removed. The refractory organic compounds were primarily removed in ZVI process of the integrated system. These compounds, with molecular weights either ranged 10,000-30,000 Da or 0-2000 Da, were mainly the humic acid (HA) and hydrophilic (HyI) compounds. Oxidation-reduction and coagulation were the main removal mechanisms in ZVI process, which could enhance the biodegradability of the system effluent. Furthermore, the integrated system showed a rapid recovery performance against the sudden loading shock and remained high efficiencies for pollutants removal. Overall, the integrated system was proved feasible for coking wastewater treatment in practical applications.     

Nitrate reduction over nanoscale zero-valent iron prepared by hydrogen reduction of goethite

Nitrate reduction with nanoscale zero-valent iron (NZVI) was reported as a potential technology to remove nitrate from nitrate-contaminated water. In this paper, nitrate reduction with NZVI prepared by hydrogen reduction of natural goethite (NZVI-N, -N represents natural goethite) and hydrothermal goethite (NZVI-H, -H represents hydrothermal goethite) was conducted. Besides, the effects of reaction time, nitrate concentration, iron-to-nitrate ratio on nitrate removal rate over NZVI-H and NZVI-N were investigated. To prove their excellent nitrate reduction capacities, NZVI-N and NZVI-H were compared with ordinary zero-valent iron (OZVI-N) through the static experiments. Based on all above investigations, the mechanism of nitrate reduction with NZVI-N was proposed. The result showed that reaction time, nitrate concentration, iron-to-nitrate ratio played an important role in nitrate reduction by NZVI-N and NZVI-H. Compared with OZVI, NZVI-N and NZVI-H showed little relationship with pH. And NZVI-N for nitrate composition offers a higher stability than NZVI-H because of the existence of Al-substitution. Furthermore, NZVI-N, prepared by hydrogen reduction of goethite, has higher activity for nitrate reduction and the products contain hydrogen, nitrogen, NH₄⁺, a little nitrite, but no NOx, meanwhile NZVI-N was oxidized to Fe²⁺. It is a relatively easy and cost-effective method for nitrate removal, so NZVI-N reducing nitrate has a great potential application in nitrate removal of groundwater.     

Kinetics of zero-valent iron reductive transformation of the anthraquinone dye Reactive Blue 4

The effect of operational conditions and initial dye concentration on the reductive transformation (decolorization) of the textile dye Reactive Blue 4 (RB4) using zero-valent iron (ZVI) filings was evaluated in batch assays. The decolorization rate increased with decreasing pH and increasing temperature, mixing intensity, and addition of salt (100 g L⁻¹ NaCl) and base (3 g L⁻¹ Na₂CO₃ and 1 g L⁻¹ NaOH), conditions typical of textile reactive dyebaths. ZVI RB4 decolorization kinetics at a single initial dye concentration were evaluated using a pseudo first-order model. Under dyebath conditions and at an initial RB4 concentration of 1000 mg L⁻¹, the pseudo first-order rate constant (k_obs) was 0.029 ± 0.006 h⁻¹, corresponding to a half-life of 24.2 h and a ZVI surface area-normalized rate constant (k_SA) of 2.9 × 10⁻⁴ L m⁻² h⁻¹. However, as the initial dye concentration increased, the k_obs decreased, suggesting saturation of ZVI surface reactive sites. Non-linear regression of initial decolorization rate values as a function of initial dye concentration, based on a reactive sites saturation model, resulted in a maximum decolorization rate (V_m) of 720 ± 88 mg L⁻¹ h⁻¹ and a half-saturation constant (K) of 1299 ± 273 mg L⁻¹. Decolorization of RB4 via a reductive transformation, which was essentially irreversible (2–5% re-oxidation), is believed to be the dominant decolorization mechanism. However, some degree of RB4 irreversible sorption cannot be completely discounted. The results of this study show that ZVI treatment is a promising technology for the decolorization of commercial, anthraquinone-bearing, spent reactive dyebaths.     

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

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

Detoxification of PAX-21 ammunitions wastewater by zero-valent iron for microbial reduction of perchlorate

US Army and the Department of Defense (DoD) facilities generate perchlorate (ClO₄⁻) from munitions manufacturing and demilitarization processes. Ammonium perchlorate is one of the main constituents in Army's new main charge melt-pour energetic, PAX-21. In addition to ammonium perchlorate, hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) and 2,4-dinitroanisole (DNAN) are the major constituents of PAX-21. In order to evaluate microbial perchlorate reduction as a practical option for the treatment of perchlorate in PAX-21 wastewater, we conducted biodegradation experiments using glucose as the primary sources of electrons and carbon. Batch experiments showed that negligible perchlorate was removed in microbial reactors containing PAX-21 wastewater while control bottles containing seed bacteria and glucose rapidly and completely removed perchlorate. These results suggested that the constituents in PAX-21 wastewater may be toxic to perchlorate reducing bacteria. A series of batch toxicity test was conducted to identify the toxic constituents in PAX-21 and DNAN was identified as the primary toxicant responsible for inhibiting the activity of perchlorate reducing bacteria. It was hypothesized that pretreatment of PAX-21 by zero-valent iron granules will transform toxic constituents in PAX-21 wastewater to non-toxic products. We observed complete reduction of DNAN to 2,4-diaminoanisole (DAAN) and RDX to formaldehyde in abiotic iron reduction study. After a 3-day acclimation period, perchlorate in iron-treated PAX-21 wastewater was rapidly decreased to an undetectable level in 2 days. This result demonstrated that iron treatment not only removed energetic compounds but also eliminated the toxic constituents that inhibited the subsequent microbial process.     

Enhancement of electrokinetic remediation of hyper-Cr(VI) contaminated clay by zero-valent iron

This paper investigated the effectiveness of incorporating zero-valent iron (ZVI) into electrokinetic (EK) to remediate hyper-Cr(VI) contaminated clay (2497 mg/kg). A ZVI wall was installed in the center of the soil specimen and was filled with 1:1 (w/w) ratio of granular ZVI and sand. Results show that transport of H(+) is greatly retarded by the strong opposite migration of anionic chromate ions, whereupon a revered electroosmosis flow (EO) was resulted and alkaline zone across the specimen was developed promoting the release of Cr(VI) from the clay. Chromium removal was characterized by high Cr(VI) concentration occurred in the anolyte and the presence of Cr(III) precipitates in the catholyte. The Cr(VI) reduction efficiencies for the process without ZVI wall were 68.1 and 79.2% for 1 and 2V/cm, respectively. As ZVI wall was installed, the corresponding reduction efficiencies increased to 85.8 and 92.5%. The costs for energy and ZVI utilized in this process are US$ 41.0 and 57.5 per cubic meter for the system with electric gradient of 1 and 2V/cm, respectively. The role of ZVI wall effectively reducing Cr(VI) contamination and the operation simultaneous collection of Cr(VI) from the electrode reservoirs are two major advantages of this process.     

Dechlorination of atrazine using zero-valent iron (Fe0) under neutral pH conditions

Zero-valent iron (Fe0) is frequently used for the dechlorination of pesticides, because it is economical, easily acquired and stable. The kinetics of dechlorination by Fe0 are improved at low pH, but this requires additional acid addition, while dechlorination hardly occurs under basic conditions. Due to the buffer capacity of geological materials such as clay and sediment, however, the addition of acid to obtain a low pH may not be effective. In this research, the dechlorination constants of atrazine by Fe0 were measured with the addition of buffer solution to simulate the buffer capacity of sediment. In the presence of the buffer solution, the pH values remained neutral, while dechlorination occurred more slowly than that observed under acid additions but faster than that without any buffer. When the initial concentrations of atrazine were 10mg/L, 30 mg/L, and 50mg/L, its dechlorination was explained using pseudo-first order reaction kinetics. The pseudo-first order constants were 3.01 x 10(-2)d(-1) at 10 mg/L, 3.23 x 10(-2)d(-1) at 30 mg/L and 3.38 x 10(-2)d(-1) at 50mg/L. In addition, the half-lives of atrazine were 8.91 d at 10mg/L, 9.32 d at 30 mg/L, and 10.00 d at 50mg/L. Acid addition may not be omitted to obtain acidic pH conditions when dechlorination is necessary in geologic materials.     

Oxidation of polyvinyl alcohol by persulfate activated with heat,Fe, and zero-valent iron

The oxidation of polyvinyl alcohol (PVA) by persulfate (S₂O₈²⁻) activated with heat, Fe²⁺, and zero-valent iron (Fe(0)) was investigated via batch experiments. It was hypothesized that elevated temperature and the addition of Fe²⁺ or Fe(0) into a persulfate-water system could enhance the oxidation of PVA by activated persulfate. Increasing the temperature from 20 to 60 °C or 80 °C accelerated the oxidation rate of PVA, which achieved complete oxidation in 30 and 10 min, respectively. At 20 °C, the addition of Fe²⁺ or Fe(0) to the persulfate-water system significantly enhanced the oxidation of PVA. The optimal persulfate-to-Fe²⁺ or Fe(0) molar ratio was found to be 1:1. Complete oxidation of PVA was obtained by Fe(0)-activated persulfate in 2 h. Synergistic activation of persulfate by heat and Fe²⁺ or Fe(0) was also shown to enhance the oxidation of PVA in the persulfate-water system. By using GC–MS analysis, an oxidation product of PVA was identified as vinyl acetic acid (C₄H₆O₂), which is readily biodegradable. Our results suggest that the oxidative treatment of PVA by activated persulfate is a viable option for the pretreatment of PVA-laden wastewater to enhance its biodegradability.     

A radiotracer study of the adsorption behavior of aqueous Ba(2+) ions on nanoparticles of zero-valent iron

Recently, iron nanoparticles are increasingly being tested as adsorbents for various types of organic and inorganic pollutants. In this study, nanoparticles of zero-valent iron (NZVI) synthesized under atmospheric conditions were employed for the removal of Ba(2+) ions in a concentration range 10(-3) to 10(-6) M. Throughout the study, (133)Ba was used as a tracer to study the effects of time, concentration, and temperature. The obtained data was analyzed using various kinetic models and adsorption isotherms. Pseudo-second-order kinetics and Dubinin-Radushkevich isotherm model provided the best correlation with the obtained data. Observed thermodynamic parameters showed that the process is exothermic and hence enthalpy-driven.     

Removal of heavy metal lead(II) using nanoscale zero-valent iron with different preservation methods

In this study, different nanoscale zero-valent irons (nZVI) were prepared in order to improve their stability and reactivity to heavy metal lead (Pb (II)). The composition, particle size and morphology of obtained nZVI were characterized by X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), scanning electron microscope (SEM). The effects of nZVI dosage, pH, initial Pb (II) concentration and reaction time on the removal efficacy of Pb (II) were investigated. The results show that undried nZVI has more active sites due to its weaker oxidation, and thus the removal efficiency of Pb(II) by undried nZVI was higher than that by dried nZVI. As a result, the same removal efficiency could be achieved with the use of less undried nZVI for the identical concentration of Pb(II). Furthermore, the experimental procedure could be apparently simplified, which eliminates the steps of washing, separation and dehydration compared with the traditional preparation method. The experimental data could be well fitted by the Langmuir adsorption isotherm model, and the maximum adsorption capacity of dried and undried nZVI is 671.14 and 807.23?mg·g^?1 at pH 6, respectively. The experimental data followed the pseudo second-order kinetic model with a kinetic constant of 7.65?×?10^?4 and 1.39?×?10^?3 for undried and dried nZVI, respectively. In conclusion, undried nZVI had high adsorption capacity and adsorption rate for Pb(II) in the solution.     

Fine structure characterization of zero-valent iron nanoparticles for decontamination of nitrites and nitrates in wastewater and groundwater

The main objectives of the present study were to investigate the chemical reduction of nitrate or nitrite species by zero-valent iron nanoparticle (ZVIN) in aqueous solution and related reaction kinetics or mechanisms using fine structure characterization. This work also exemplifies the utilization of field emission-scanning electron microscope (FE–SEM), transmission electron microscopy (TEM), and x-ray diffraction (XRD) to reveal the speciation and possible reaction pathway in a very complex adsorption and redox reaction process. Experimentally, ZVIN of this study was prepared by sodium borohydride reduction method at room temperature and ambient pressure. The morphology of as-synthesized ZVIN shows that the nearly ball and ultrafine particles ranged of 20–50 nm were observed with FE–SEM or TEM analysis. The kinetic model of nitrites or nitrates reductive reaction by ZVIN is proposed as a pseudo first-order kinetic equation. The nitrite and nitrate removal efficiencies using ZVIN were found 65–83% and 51–68%, respectively, based on three different initial concentrations. Based on the XRD pattern analyses, it is found that the quantitative relationship between nitrite and Fe(III) or Fe(II) is similar to the one between nitrate and Fe(III) in the ZVIN study. The possible reason is due to the faster nitrite reduction by ZVIN. In fact, the occurrence of the relative faster nitrite reductive reaction suggested that the passivation of the ZVIN have a significant contribution to iron corrosion. The extended x-ray absorption fine structure (EXAFS) or x-ray absorption near edge structure (XANES) spectra show that the nitrites or nitrates reduce to N₂ or NH₃ while oxidizing the ZVIN to Fe₂O₃ or Fe₃O₄ electrochemically. It is also very clear that decontamination of nitrate or nitrite species in groundwater via the in-situ remediation with a ZVIN permeable reactive barrier would be environmentally attractive.     

Fine structure characterization of zero-valent iron nanoparticles for decontamination of nitrites and nitrates in wastewater and groundwater

Abstract

The main objectives of the present study were to investigate the chemical reduction of nitrate or nitrite species by zero-valent iron nanoparticle (ZVIN) in aqueous solution and related reaction kinetics or mechanisms using fine structure characterization. This work also exemplifies the utilization of field emission-scanning electron microscope (FE–SEM), transmission electron microscopy (TEM), and x-ray diffraction (XRD) to reveal the speciation and possible reaction pathway in a very complex adsorption and redox reaction process. Experimentally, ZVIN of this study was prepared by sodium borohydride reduction method at room temperature and ambient pressure. The morphology of as-synthesized ZVIN shows that the nearly ball and ultrafine particles ranged of 20–50 nm were observed with FE–SEM or TEM analysis. The kinetic model of nitrites or nitrates reductive reaction by ZVIN is proposed as a pseudo first-order kinetic equation. The nitrite and nitrate removal efficiencies using ZVIN were found 65–83% and 51–68%, respectively, based on three different initial concentrations. Based on the XRD pattern analyses, it is found that the quantitative relationship between nitrite and Fe(III) or Fe(II) is similar to the one between nitrate and Fe(III) in the ZVIN study. The possible reason is due to the faster nitrite reduction by ZVIN. In fact, the occurrence of the relative faster nitrite reductive reaction suggested that the passivation of the ZVIN have a significant contribution to iron corrosion. The extended x-ray absorption fine structure (EXAFS) or x-ray absorption near edge structure (XANES) spectra show that the nitrites or nitrates reduce to N₂ or NH₃ while oxidizing the ZVIN to Fe₂O₃ or Fe₃O₄ electrochemically. It is also very clear that decontamination of nitrate or nitrite species in groundwater via the in-situ remediation with a ZVIN permeable reactive barrier would be environmentally attractive.