Highly Selective Reduction of Nitrate by Zero-Valent Aluminum (ZVAI) Ball-Milled Materials at Circumneutral pH: Important Role of Microgalvanic Cells for Depassivation of ZVAl and N2-Selectivity.

The passivation of zero-valent aluminum (ZVAl) limits its application in environmental remediation. Herein, a ternary composite material Al-Fe-AC is synthesized via a ball-milling treatment on a mixture of Al0, Fe0, and activated carbon (AC) powders. The results show that the as-prepared micronsized Al-Fe-AC powder could achieve highly efficient nitrate removal and a nitrogen (N2)-selectivity of >75%. The mechanism study reveals that, in the initial stage, numerous Al//AC and Fe//AC microgalvanic cells in the Al-Fe-AC material could lead to a local alkaline environment in the vicinity of the AC cathodes. The local alkalinity depassivated the Al0 component and enabled its continuous dissolution in the subsequent second stage of reaction. The functioning of the AC cathode of the Al//AC microgalvanic cell is revealed as the primary reason accounting for the highly selective reduction of nitrate. The investigation on the mass ratio of raw materials manifested that an Al/Fe/AC mass ratio of 1:1:5 or 1:3:5 was preferable. The test in simulated groundwater suggested that the as-prepared Al-Fe-AC powder could be injected into aquifers to achieve a highly selective reduction of nitrate to nitrogen. This study provides a feasible method to develop high-performance ZVAl-based remedial materials that could work in a wider pH range.

Concentration-Dependent Enhancing Effect of Dissolved Silicate on the Oxidative Degradation of Sulfamethazine by Zero-Valent Iron under Aerobic Conditions.

Dissolved silicate, as a ubiquitous inorganic component in natural waters, is reported to depress the reactivity of zero-valent iron (ZVI) for reductive reactions under anoxic conditions, but it is unclear if the same inhibitory effect occurs for a ZVI/O2 system. In this study, the role of dissolved silicate for the reactivity of micron-sized ZVI (mZVI) was revisited under aerobic conditions, and different observations were found. Silicate had a volcano-type enhancing effect on the performance of the ZVI/O2 system for sulfamethazine (SMT) degradation. The results showed that, under a circum-neutral or alkaline pH condition (pH 6.0-9.0), the presence of dissolved silicate could significantly enhance the degradation of SMT because silicate coordinated with ferrous ions and further led to the generation of reactive oxygen species (ROS). This study suggests that silicate can act as both a ligand and corrosion inhibitor in a ZVI/O2 system: the coordination of silicate and ferrous iron accelerated the oxidative degradation of organic pollutants in an oxic aqueous solution, while the corrosion inhibitory effect of surface-bound silicate at higher concentrations may decrease the reactivity of the ZVI/O2 system, thereby offsetting the enhancing effect from the silicate-coordinated ferrous iron. This study not only redefines the role of naturally occurring silicate for a ZVI reaction system but also gives clues to develop high-efficiency ZVI/O2 technologies for water remediation.

Dissolved Silicate Enhances the Oxidation of Chlorophenols by Permanganate: Important Role of Silicate-Stabilized MnO2 Colloids.

Dissolved silicate is an important background constituent of natural waters, but there is little clarity regarding the effect of silicate on the oxidizing capability of permanganate (Mn(VII)) and on its efficiency for remediation applications. In the present study, we found that dissolved silicate, metasilicate or disilicate (DS), could significantly promote the oxidation of 2,4-dichlorophenol (2,4-DCP) by Mn(VII), and the extent of the promoting effect was even more evident than that of pyrophosphate (PP). The experiments showed that, unlike PP, DS was not capable of coordinating with Mn(III) ions, and the promoting effect of DS was not due to the oxidizing capability of complexed Mn(III). Instead, DS ions, as a weak base, could combine with the hydroxyl groups of MnO2 via hydrogen bonding to limit the growth of colloidal MnO2 particles. The DS-stabilized colloidal MnO2 particles, with hydrodynamic diameters less than 100 nm, could act as catalysts to enhance the oxidation of 2,4-DCP by Mn(VII). The best promoting effect of DS on the performance of Mn(VII) oxidant was achieved at the initial solution pH of 7, and the coexisting bicarbonate ions further improved the oxidation of 2,4-DCP in the Mn(VII)/DS system. Sand column experiments showed that the combined use of Mn(VII) and DS additive could mitigate the problem of permeability reduction of sand associated with the retention of MnO2 particles. This study not only deepens our understanding on the role of dissolved silicate in a Mn(VII) oxidation process but also provides an effective and green method to enhance the oxidizing capacity of Mn(VII)-based treatment systems.

Understanding the electrode reaction process of dechlorination of 2,4-dichlorophenol over Ni/Fe nanoparticles: Effect of pH and 2,4-dichlorophenol concentration.

Herein, with the exploitation of iron and nickel electrodes, the 2,4-dichlorophenol (2,4-DCP) dechlorinating processes at the anode and cathode, respectively, were separately studied via various electrochemical techniques (e.g., Tafel polarization, linear polarization, electrochemical impedance spectroscopy). With this in mind, Ni/Fe nanoparticles were prepared by chemical solution deposition, and utilized to test the dechlorination activities of 2,4-DCP over a bimetallic system. For the iron anode, the results showed that higher 2,4-DCP concentration and solution acidity aggravated the corrosion within the electrode. The charge transfer resistance (Rct) values of the iron electrode were 703, 473, 444, and 437 Ω∙cm2 for the initial 2,4-DCP concentrations of 0, 20, 50, and 80 mg/L, respectively. When the bulk pH of the 2,4-DCP solution varied from 3.0, 5.0 to 7.0, the corresponding Rct values were 315, 376, and 444 Ω∙cm2, respectively. For the nickel cathode, the reduction current densities on the electrode at -0.75 V (vs. saturated calomel electrode) were 80, 106, and 111 µA/cm2, for initial 2,4-DCP concentrations of 40, 80, and 125 mg/L. The dechlorination experiments demonstrated that when the initial pH of the solution was 7.0, 5.0, and 3.0, the dechlorination percentage of 2,4-DCP by Ni/Fe nanoparticles was 62%, 69%, and 74%, respectively, which was in line with the electrochemical experiments. 10 wt.% Ni loading into Ni/Fe bimetal was affordable and gave a good dechlorination efficiency of 2,4-DCP, and fortunately the Ni/Fe nanoparticles remained comparatively stable in the dechlorination processes at pH 3.0.

Disilicate-Assisted Iron Electrolysis for Sequential Fenton-Oxidation and Coagulation of Aqueous Contaminants.

Sodium disilicate (SD), an inorganic and environmentally friendly ligand, is introduced into the conventional iron electrolysis system to achieve an oxidizing Fenton process to degrade organic pollutants. Electrolytic ferrous ions, which are complexed by the disilicate ions, can chemically reduce dioxygen molecules via consecutive reduction steps, producing H2O2 for the Fenton-oxidation of organics. At the near-neutral pH (from 6 to 8), the disilicate-Fe(II) complexes possess strong reducing capabilities; therefore, a near-neutral pH rather than an acid condition is preferable for the disilicate-assisted iron electrolysis (DAIE) process. Following the DAIE process, the different complexing capacities of disilicate for ferrous/ferric ions and calcium ions can be used to break the disilicate-iron complexes. The addition of CaO or CaCl2 can precipitate ferrous/ferric ions, disilicates and possibly heavy metals in the wastewater. Compared to previously reported organic and phosphorus ligands, SD is a low-cost inorganic agent that does not lead to secondary pollution, and would not compete with the target organic pollutants for •OH; therefore, it would greatly expand the application fields of the O2 activation process. The combination of DAIE and CaO treatments is envisioned to be a versatile and affordable method for treating wastewater with complicated pollutants (e.g., mixtures of biorefractory organics and heavy metals).

Effect of Arsenic on the Formation and Adsorption Property of Ferric Hydroxide Precipitates in ZVI Treatment.

Treatment of arsenic by zerovalent iron (ZVI) has been studied extensively. However, the effect of arsenic on the formation of ferric hydroxide precipitates in the ZVI treatment has not been investigated. We discovered that the specific surface area (ca. 187 m2/g) and arsenic content (ca. 67 mg/g) of the suspended solids (As-containing solids) generated in the ZVI treatment of arsenic solutions were much higher than the specific surface area (ca. 37 m2/g) and adsorption capacity (ca.12 mg/g) of the suspended solids (As-free solids) generated in the arsenic-free solutions. Arsenic in the As-containing solids was much more stable than the adsorbed arsenic in As-free solids. XRD, SEM, TEM, and selected area electron diffraction (SAED) analyses showed that the As-containing solids consisted of amorphous nanoparticles, while the As-free solids were composed of micron particles with weak crystallinity. Extended X-ray absorption fine structure (EXAFS) analysis determined that As(V) was adsorbed on the As-containing suspended solids and magnetic solid surfaces through bidentate binuclear complexation; and As(V) formed a mononuclear complex on the As-free suspended solids. The formation of the surface As(V) complexes retarded the bonding of free FeO6 octahedra to the oxygen sites on FeO6 octahedral clusters and prevented the growth of the clusters and their development into 3-dimensional crystalline phases.

Increased Electron-Accepting and Decreased Electron-Donating Capacities of Soil Humic Substances in Response to Increasing Temperature.

The electron transfer capacities (ETCs) of soil humic substances (HSs) are linked to the type and abundance of redox-active functional moieties in their structure. Natural temperature can affect the chemical structure of natural organic matter by regulating their oxidative transformation and degradation in soil. However, it is unclear if there is a direct correlation between ETC of soil HS and mean annual temperature. In this study, we assess the response of the electron-accepting and -donating capacities (EAC and EDC) of soil HSs to temperature by analyzing HSs extracted from soil set along glacial-interglacial cycles through loess-palaeosol sequences and along natural temperature gradients through latitude and altitude transects. We show that the EAC and EDC of soil HSs increase and decrease, respectively, with increasing temperature. Increased temperature facilitates the prevalence of oxidative degradation and transformation of HS in soils, thus potentially promoting the preferentially oxidative degradation of phenol moieties of HS or the oxidative transformation of electron-donating phenol moieties to electron-accepting quinone moieties in the HS structure. Consequently, the EAC and EDC of HSs in soil increase and decrease, respectively. The results of this study could help to understand biogeochemical processes, wherein the redox functionality of soil organic matter is involved in the context of increasing temperature.

Molten salt CO2 capture and electro-transformation (MSCC-ET) into capacitive carbon at medium temperature: effect of the electrolyte composition.

Electrochemical transformation of CO2 into functional materials or fuels (i.e., carbon, CO) in high temperature molten salts has been demonstrated as a promising way of carbon capture, utilisation and storage (CCUS) in recent years. In a view of continuous operation, the electrolysis process should match very well with the CO2 absorption kinetics. At the same time, in consideration of the energy efficiency, a molten salt electrochemical cell running at lower temperature is more beneficial to a process powered by the fluctuating renewable electricity from solar/wind farms. Ternary carbonates (Li : Na : K = 43.5 : 31.5 : 25.0) and binary chlorides (Li : K = 58.5 : 41.5), two typical kinds of eutectic melt with low melting points and a wide electrochemical potential window, could be the ideal supporting electrolyte for the molten salt CO2 capture and electro-transformation (MSCC-ET) process. In this work, the CO2 absorption behaviour in Li2O/CaO containing carbonates and chlorides were investigated on a home-made gas absorption testing system. The electrode processes as well as the morphology and properties of carbon obtained in different salts are compared to each other. It was found that the composition of molten salts significantly affects the absorption of CO2, electrode processes and performance of the product. Furthermore, the relationship between the absorption and electro-transformation kinetics are discussed based on the findings.

Kinetic and Thermodynamic Characterization of Enhanced Carbon Dioxide Absorption Process with Lithium Oxide-Containing Ternary Molten Carbonate.

Efficient and high-flux capture of CO2 is the prerequisite of its utilization. Static absorption of CO2 with solid Li2O and molten salts (Li2O-free and Li2O-containing Li-Na-K carbonates) was investigated using a reactor with in situ pressure monitoring. The absorption capacity of dissolved Li2O was 0.835 molCO2/molLi2O at 723 K, larger than that of solid Li2O. For the solid Li2O absorbents, formation of solid Li2CO3 on the surface can retard the further reactions between Li2O and CO2, whereas the dissociation/dissolution effect of molten carbonate on Li2O improved the mass-specific absorption capacity of liquid Li2O. In Li2O-containing Li-Na-K molten carbonate, CO2 was mostly absorbed by alkaline oxide ions (O2-). The chemical interactions between CO2 and CO32- contributed to CO2 uptake via formation of multiple carbonate ions. The mass transfer of these absorbing ions was found as the dominating factor governing the rate of static absorption. Higher temperatures reduced the thermodynamic tendency of CO2 absorption, but a lower viscosity at elevated temperature was conducive to absorption kinetics. Compared with the commonly used CaO absorbent, Li2O was much more dissolvable in molten carbonate. The Li2O-containing molten carbonate is potentially a promising medium for industrial carbon capture and electrochemical transformation process.

Sulfur doped reduced graphene oxides with enhanced catalytic activity for oxygen reduction via molten salt redox-sulfidation.

A spontaneous redox reaction of reduced graphene oxide (rGO) in molten Li2CO3-Na2CO3-K2CO3 with a small amount of Li2SO4 at 550 °C was applied to synthesize sulfur and sulfur-cobalt doped rGOs (S-rGO/S-Co-rGO). The obtained S-rGOs and S-Co-rGOs show enhanced catalytic activity for the oxygen reduction reaction (ORR) in alkaline aqueous solutions. The onset reduction potential and the half-wave potential of S-Co-rGO are 60 and 40 mV more positive than those of the original rGO, respectively. The reduction current density of S-Co-rGO increases by nearly five times. This study provides a green and continuous molten salt doping approach for the fabrication of heteroatom-doped graphene with excellent catalytic activity for the ORR.

Iron electrolysis-assisted peroxymonosulfate chemical oxidation for the remediation of chlorophenol-contaminated groundwater.

BACKGROUND: Electrolysis with an iron anode is a novel way to provide ferrous activators for chemical oxidation. The objective of this study is to evaluate the performance of peroxymonosulfate (PMS) for chlorophenol destruction when compared with H2O2 and persulfate (PS), and to see whether the electrolysis mode facilitates the buildup of conditions that favor the activation of PMS and removal of chlorophenols. RESULTS: Ferrous species can effectively activate the PMS over a wide pH range. In comparison with H2O2 and PS, PMS is less sensitive to the solution's pH and possesses stronger oxidation capability at alkaline pHs. The optimal molar ratio of PMS to Fe(II) activator is 1:1 for the destruction of 2,4-dichlorophenol (2,4-DCP). The column experiments show that an acidic zone developed downstream from the anode is favorable to maintain ferrous ions and subsequent activation of PMS. The reactivity of the PMS can be manipulated by varying the electrical currents, and the process demonstrates effectiveness for treating organic contaminants. 2,4-DCP contaminated groundwater shows decreased biotoxicity after the chemical oxidation process without considering the residual PMS. CONCLUSIONS: Iron electrolysis-assisted peroxymonosulfate chemical oxidation can effectively treat the 2,4-dichlorophenol and mixtures of organic contaminants. This process can be engineered as an in situ chemical oxidation method for groundwater remediation.

Harvesting capacitive carbon by carbonization of waste biomass in molten salts.

Conversion of waste biomass to value-added carbon is an environmentally benign utilization of waste biomass to reduce greenhouse gas emissions and air pollution caused by open burning. In this study, various waste biomasses are converted to capacitive carbon by a single-step molten salt carbonization (MSC) process. The as-prepared carbon materials are amorphous with oxygen-containing functional groups on the surface. For the same type of waste biomass, the carbon materials obtained in Na2CO3-K2CO3 melt have the highest Brunauer-Emmett-Teller (BET) surface area and specific capacitance. The carbon yield decreases with increasing reaction temperature, while the surface area increases with increasing carbonization temperature. A working temperature above 700 °C is required for producing capacitive carbon. The good dissolving ability of alkaline carbonate molten decreases the yield of carbon from waste biomasses, but helps to produce high surface area carbon. The specific capacitance data confirm that Na2CO3-K2CO3 melt is the best for producing capacitive carbon. The specific capacitance of carbon derived from peanut shell is as high as 160 F g(-1) and 40 µF cm(-2), and retains 95% after 10,000 cycles at a rate of 1 A g(-1). MSC offers a simple and environmentally sound way for transforming waste biomass to highly capacitive carbon as well as an effective carbon sequestration method.

Effects of reduced sulfur compounds on Pd-catalytic hydrodechlorination of trichloroethylene in groundwater by cathodic H2 under electrochemically induced oxidizing conditions.

Reduced sulfur compounds (RSCs) poison Pd catalysts for catalytic hydrodechlorination of contaminants in anoxic groundwater. This study investigates the effects of RSCs on Pd-catalytic hydrodechlorination of trichloroethylene (TCE) in oxic groundwater. Water electrolysis in an undivided electrolytic cell is used to produce H2 for TCE hydrodechlorination under oxidizing conditions. TCE is efficiently hydrodechlorinated to ethane, with significant accumulation of H2O2 under acidic conditions. The presence of sulfide at concentrations less than 93.8 µM moderately inhibits TCE hydrodechlorination and H2O2 production. The presence of sulfite at low concentrations (≤1 mM) significantly enhances TCE decay, while at high concentration (3 mM) inhibits initially and enhances afterward when sulfite concentration declines to less than 1 mM. Using radical scavenging experiments and an electron spin resonance assay, SO3(•-), which is generated from sulfite under oxidizing conditions, is validated as the new reactive species contributing to the enhancement. This study reveals a distinct mechanism of effect of sulfite on TCE hydrodechlorination by Pd and H2 in oxic groundwater and presents an alternative approach to increasing resistance of Pd to RSCs poisoning.

Propylene glycol-mixed steam enhanced extraction for an efficient and sustainable remediation of PAHs-contaminated soil.

An innovative thermal desorption method, propylene glycol (PG)-mixed steam enhanced extraction, is proposed for a highly efficient remediation of polycyclic aromatic hydrocarbons (PAHs)-contaminated soil. It is found that injecting PG-mixed steam into soil column could obtain > 99% removal efficiencies of PAHs either for the pyrene-spiked soil, or for the contaminated field soil with high-molecular-weight PAHs. PG is a safe and low-cost dihydric alcohol with a boiling point higher than water. When the PG-mixed steam penetrated the contaminated soil, the PG vapor preferentially condensed to form a hot liquid with concentrated PG (e.g., from 30 wt% PG in gas phase to 90 wt% PG in the liquid phase), which would significantly solubilize the PAHs and enhance their desorption from soils. The results also revealed that the effluents derived from the PG-mixed steam could be purified by removing the desorbed PAHs using a simple coagulation treatment, and the recovered PG solution could be reused. The plant assay using wheat seeds showed that the remediated soil had a good regreening potential. Our results demonstrate that PG-mixed steam injection is a promising thermal desorption method for an efficient and sustainable remediation of PAHs-contaminated soil.

New insights into engineering the core size and carbon shell thickness of Co@C core-shell catalysts for efficient and stable Fenton-like catalysis.

Herein, we engineered the cobalt core size and carbon shell thickness of Co@C by molten salt electrolysis (MSE) to investigate the enhanced essence of decreasing core size as well as the shell thickness dependence-mediated transition of catalytic mechanisms. We found that the reaction activation energy (RAE) of Co@C/peroxymonosulfate (PMS) systems was intimately dependent on the core sizes for sulfamethoxazole (SMX) degradation. The smaller core size of 26 nm provided a lower RAE of 13.39 kJ mol-1. In addition, increasing carbon shell thicknesses of Co@C altered the catalytic mechanisms from a radical pathway of SO4•- and •OH to to a non-radical pathway of 1O2 and electron-transfer process (ETP), which were verified by experimental results and density functional theory (DFT) calculations. Interestingly, increasing carbon shell thicknesses promoted the charge transfer between Co metal slab and carbon shell, increased the adsorption energy of PMS molecule on the Co@C slab, and decreased the length of OO, which favoured the occurrence of non-free radical processes.

In-situ photoreduction strategy for synthesis of silver nanoparticle-loaded PVDF ultrafiltration membrane with high antibacterial performance and stability.

Ultrafiltration (UF) technology using polyvinylidene fluoride (PVDF) membrane has been widely applied to water and wastewater treatment due to its low cost and simple operation process. However, PVDF-based UF membrane always encountered the issue of membrane biofouling that greatly impacted the filtration performance. In this study, we prepare a silver nanoparticle (AgNP)-loaded PVDF (Ag/PVDF) UF membrane by an in-situ photoreduction method to mitigate the membrane biofouling. Different from the previously reported method, AgNPs were synthesized in-situ by a UV photoreduction process, in which Ag+ ions were reduced to zero-valent Ag nanoparticles by the photo-induced reducing radicals. Antibacterial experiments showed that the inhibition efficiency of Ag/PVDF membrane to Escherichia coli reached up to ~ 99% after antibacterial treatment for 24 h. In comparison with the pristine PVDF membrane, Ag/PVDF membrane possessed a lower water contact angle (83.7° vs. 38.1°), and its pure water flux increased by 23.7%, and a high bovine serum albumin (BSA) rejection efficiency was maintained. In addition, the high stability of the Ag/PVDF composite membrane was confirmed by the extremely low releasing amount of Ag. This study provides a novel strategy for the preparation of metal nanoparticle-incorporated Ag/PVDF ultrafiltration composite membrane showing favorable antibacterial performance and stability.

Efficient activation of peroxodisulfate by novel bionic iron-encapsulated biochar: The key roles of electron transfer pathway and reactive oxygen species evolution.

In this study, a novel iron-encapsulated biochar (Fe@BC) was prepared using the biomass cultivated with an iron-containing solution. The iron in Fe@BC showed the phase change from Fe3O4 to α-Fe, and to CFe15.1, with the increase of pyrolysis temperature (500-900 °C), and a graphene shell formed on the surface of Fe@BC. In addition, the signals assigned to the π-π* shake up, pyridinic N, graphitic N, and defects of Fe@BC were found to be stronger as the pyrolysis temperature increased. The F4@B9 sample, which was prepared at 900 °C, exhibited an excellent performance (98.01 %) to activate peroxydisulfate (PDS) for the degradation of 2,4-dichlorophenol. Electron paramagnetic resonanceand chemical quenching experiments revealed that reactive oxygen radicals (ROS) including sulfate radical (•SO4-), hydroxyl radical (•OH), superoxide radical (•O2-), and singlet oxygen (1O2) existed in the F4@B9/PDS system. Furthermore, the micro-electrolysis process facilitated the generation of •O2- (12.35 %) and 1O2 (6.49 %) compared with the pure PDS system. Density functional theory revealed that, for the F4@B9-activated PDS process, the graphene shell of F4@B9 served as catalytic active sites as well. According to the correlation analysis, the iron specie of CFe15.1 was more favorable for the generation of ROS than α-Fe. Also, π-π* shake up, pyridinic N, graphitic N, and defects participated in the PDS activation. This study provides a new method for the preparation of high-performance catalysts from naturally grown biomass with high iron contents.

Efficient degradation of TCE in groundwater using Pd and electro-generated H2 and O2: a shift in pathway from hydrodechlorination to oxidation in the presence of ferrous ions.

Degradation of trichloroethylene (TCE) in simulated groundwater by Pd and electro-generated H(2) and O(2) is investigated in the absence and presence of Fe(II). In the absence of Fe(II), hydrodechlorination dominates TCE degradation, with accumulation of H(2)O(2) up to 17 mg/L. Under weak acidity, low concentrations of oxidizing •OH radicals are detected due to decomposition of H(2)O(2), slightly contributing to TCE degradation via oxidation. In the presence of Fe(II), the degradation efficiency of TCE at 396 µM improves to 94.9% within 80 min. The product distribution proves that the degradation pathway shifts from 79% hydrodechlorination in the absence of Fe(II) to 84% •OH oxidation in the presence of Fe(II). TCE degradation follows zeroth-order kinetics with rate constants increasing from 2.0 to 4.6 µM/min with increasing initial Fe(II) concentration from 0 to 27.3 mg/L at pH 4. A good correlation between TCE degradation rate constants and •OH generation rate constants confirms that •OH is the predominant reactive species for TCE oxidation. Presence of 10 mM Na(2)SO(4), NaCl, NaNO(3), NaHCO(3), K(2)SO(4), CaSO(4), and MgSO(4) does not significantly influence degradation, but sulfite and sulfide greatly enhance and slightly suppress degradation, respectively. A novel Pd-based electrochemical process is proposed for groundwater remediation.

Electrochemically induced dual reactive barriers for transformation of TCE and mixture of contaminants in groundwater.

A novel reactive electrochemical flow system consisting of an iron anode and a porous cathode is proposed for the remediation of mixture of contaminants in groundwater. The system consists of a series of sequentially arranged electrodes, a perforated iron anode, a porous copper cathode followed by a mesh-type mixed metal oxide anode. The iron anode generates ferrous species and a chemically reducing environment, the porous cathode provides a reactive electrochemically reducing barrier, and the inert anode provides protons and oxygen to neutralize the system. The redox conditions of the electrolyte flowing through this system can be regulated by controlling the distribution of the electric current. Column experiments are conducted to evaluate the process and study the variables. The electrochemical reduction on a copper foam cathode produced an electrode-based reductive potential capable of reducing TCE and nitrate. Rational electrodes arrangement, longer residence time of electrolytes and higher surface area of the foam electrode improve the reductive transformation of TCE. More than 82.2% TCE removal efficiency is achieved for the case of low influent concentration (<7.5 mg/L) and high current (>45 mA). The ferrous species produced from the iron anode not only enhance the transformation of TCE on the cathode, but also facilitates transformation of other contaminants including dichromate, selenate and arsenite. Removal efficiencies greater than 80% are achieved for these contaminants in flowing contaminated water. The overall system, comprising the electrode-based and electrolyte-based barriers, can be engineered as a versatile and integrated remedial method for a relatively wide spectrum of contaminants and their mixtures.

Role of Iron Anode Oxidation on Transformation of Chromium by Electrolysis.

The potential for chemical reduction of hexavalent chromium Cr(VI) in contaminated water and formation of a stable precipitate by Zero Valent Iron (ZVI) anode electrolysis is evaluated in separated electrodes system. Oxidation of iron electrodes produces ferrous ions causing the development of a reducing environment in the anolyte, chemical reduction of Cr(VI) to Cr(III) and formation of stable iron-chromium precipitates. Cr(VI) transformation rates are dependent on the applied electric current density. Increasing the electric current increases the transformation rates; however, the process is more efficient under lower volumetric current density (for example 1.5 mA L(-1) in this study). The transformation follows a zero order rate that is dependent on the electric current density. Cr(VI) transformation occurs in the anolyte when the electrodes are separated as well as when the electrolytes (anolyte/catholyte) are mixed, as used in electrocoagulation. The study shows that the transformation occurs in the anolyte as a result of ferrous ion formation and the product is a stable Fe(15)Cr(5)(OH)(60) precipitate.