Reactivity Of Zero-valent Iron Research Articles

Enhancing and Sustaining Arsenic Removal in a Zerovalent Iron-based Magnetic Flow-through Water Treatment System

In areas affected by arsenicosis, zerovalent iron (ZVI)/sand filters are extensively used by households to treat groundwater, but ZVI surface passivation and filter clogging limit their arsenic (As) removal performance. Here we present a magnetic confinement-enabled column reactor coupled with periodic ultrasonic depassivation (MCCR-PUD), which efficiently and sustainably removes As by reaction with continuously generated iron (oxyhydr)oxides from ZVI oxidative corrosion. In the MCCR, ZVI microparticles self-assemble into stable millimeter-scale wires in forest-like arrays in a parallel magnetic field (0.42−0.48 T, produced by two parallel permanent magnets), forming a highly porous structure (87% porosity) with twice the accessible reactive surface area of a ZVI/sand mixture. For a feed concentration of 100 μg/L As(III), the MCCR-PUD, with a short empty bed contact time (1.6 min), treated ca. 7340 empty bed volume (EBV) of water at breakthrough (10 μg/L), 9.4 folds higher than that of a ZVI/sand filter. Due to the large interspace between ZVI wires, the MCCR-PUD effectively prevented column clogging that occurred in the ZVI/sand filter. The high water treatment capacity was attributed to the much enhanced ZVI reactivity in the magnetic field, sustained through rejuvenation by PUD. Furthermore, most of As was structurally incorporated into the produced iron (oxyhydr)oxides (mostly ferrihydrite) in the MCCR-PUD, as revealed by Mössbauer spectroscopy, X-ray absorption spectroscopy, and sequential extraction experiments. This finding evinced a different mechanism from the surface adsorption in the ZVI/sand filter. The structural incorporation of As also resulted in much less As remobilization from the produced corrosion products during aging in water, in total ∼1% in 28 days. Furthermore, the MCCR-PUD exihibted robust performance when treating complex synthetic groundwater containing natural organic matter and common ions (∼3700 EBV at breakthrough). Taken together, our study demonstrates the potential of the magnetic confinement-enabled ZVI reactor as a promising decentralized As treatment platform.

Unlocking the potential of surface modification with phosphate on ball milled zero-valent iron reactivity:Implications for radioactive metal ions removal

Numerous investigations have illuminated the profound impact of phosphate on the adsorption of uranium, however, the effect of phosphate-mediated surface modification on the reactivity of zero-valent iron (ZVI) remained enigmatic. In this study, a phosphate-modified ZVI (P-ZVIbm) was prepared with a facile ball milling strategy, and compared with ZVIbm, the U(VI) removal amount (435.2 mg/g) and efficiency (3.52×10−3 g·mg−1·min−1) of P-ZVIbm were disclosed nearly 2.0 and 54 times larger than those of ZVIbm respectively. The identification of products revealed that the adsorption mechanism dominated the removal process for ZVIbm, while the reactive modified layer strengthened both the adsorption pattern and reduction performance on P-ZVIbm. DFT calculation result demonstrated that the binding configuration shifted from bidentate binuclear to multidentate configuration, further shortening the Fe-U atomic distance. More importantly, the electron transferred is more accessible through the surface phosphate layer, and selectively donated to U(VI), accounting for the elevated reduction performance of P-ZVIbm. This investigation explicitly underscores the critical role of ZVI's surface microenvironment in the domain of radioactive metal ion mitigation and introduces a novel methodology to amplify the sequestration of U(VI) from aqueous environments.

Sulfide mediated zero valent iron for enhanced nickel removal under neutral condition: Reaction kinetic, mechanism, and stability

The application of sodium sulfide (Na2S) as sulfidation reagent of zero valent iron (ZVI) has been well studied, however, the effect of Na2S existence on ZVI reactivity remains obscure. In this study, Ni(II) removal performance, mechanism, and stability by ZVI with Na2S were investigated at neutral condition. The results showed that Ni(II) removal sharply increased from < 5–100% by ZVI within 60 min with the increase of Na2S concentration, but the subsequent Ni(II) release occurred. In addition to the slight Ni(II) removal by Na2S in aqueous phase, Ni(II) was mainly removed by the adsorption and reduction by Na2S mediated ZVI system. Characterization analysis indicated that Na2S could lead to the severe Fe0 corrosion and the main corrosion product on ZVI was lepidocrocite, which played the dominant role for Ni(II) immobilization. Meanwhile, the formation of iron sulfides on ZVI surface would enhance Ni(II) reduction and partially transform the adsorbed Ni(II) to NiS. Moreover, the higher ionic strength could further enhance the initial Ni(II) removal rate but the stability became poor. Regardless of the additive methods, the Ni(II) removal significantly enhanced in the system of ZVI and Na2S combination. Overall, this work reveals the sulfide mediated Fe0 corrosion and provides a potential method for enhancing the reactivity of ZVI in the treatment of Ni(II) pollution.

Insights into the contrasting effects of sulfidation on dechlorination of chlorinated aliphatic hydrocarbons by zero-valent iron

Contrasting effects of sulfidation on contaminants reduction by zero-valent iron (ZVI) has been reported in literature but the underlying mechanisms remain unclear. Here, under well-controlled conditions, we compared the performance of ZVI and sulfidated ZVI (S-ZVI) toward a series of chlorinated compounds. Results revealed that, although S-ZVI was more reactive than ZVI toward hexachloroethane, pentachloroethane, tetrachloroethylene, and trichloroethene, sulfidation hindered the dechlorination of the other ten tested chlorinated aliphatics by a factor of 1.5–125. Moreover, S-ZVI may lead to an accumulation of toxic partially-dechlorinated products. Analogous to its effects on ZVI reactivity, sulfidation also exerted positive, negligible, or negative effects on the electron efficiency of ZVI. Solvent kinetic isotope effect analysis suggested that direct electron transfer rather than reaction with atomic hydrogen was the dominant reduction mechanism in S-ZVI system. Hence, the sulfidation enhancing effects could be expected only when direct electron transfer is the preferred reduction route for target contaminants. Furthermore, linear free energy relationships analysis indicated one-electron reduction potential could be used to predict the transformation of chlorinated ethanes by S-ZVI, whereas for chlorinated ethenes, their adsorption properties on S-ZVI determined the dechlorination process. All these findings may offer guidance for the decision-making regarding the application of S-ZVI.

Enhancing Commercially Iron Powder Electron Transport by Surface Biosulfuration to Achieve Uranium Extraction from Uranium Ore Wastewater.

The zero-valent iron (ZVI) has attracted increasing attention due to the enhanced reactivity of ZVI to uranium wastewater. However, ZVI practical application is hampered due to its susceptibility to oxidation and the formation of passivation layers during storage and in situ restoration. To address these issues, we used a biosulfuration approach to modify ZVI for application in uranium ore wastewater treatment. A series of physicochemical characterization tools and photoelectronic analyses showed that BS-ZVI considerably increased carrier separation efficiency and visible light absorption capacity, resulting in a significant photoassisted enhancement effect on uranium extraction. Accordingly, the uranium removal efficiency of BS-ZVI reached 91% within 60 min, and its maximum adsorption capacity was 336.3 mg/g. By analyzing the mechanism, the improved U(VI) removal performance was mostly responsible on the dissolution of the passivation layer on the surface of ZVI, the generation of Fe(II) and FeS, and the important role of Shewanella putrefaciens extracellular polymers (EPS). Overall, the BS-ZVI biohybrid merges with the high activity of ZVI, bio-FeS, and self-regeneration ability of bacteria, expanding a promising new approach for sustainable treatment of uranium mine wastewater.

Hydroxylamine-assisted retarding surface passive layer of zero-valent iron for highly efficient p-nitrophenol removal via direct electron transfer

Zerovalent iron (ZVI) has been widely used in groundwater remediation due to its excellent reducibility. However, the passivation layer on ZVI surface limits the reactivity of ZVI. In this work, hydroxylamine hydrochloride (HA) has been selected to assist to improve the remediation efficiency of ZVI, and the removal rate constant of p-nitrophenol (PNP) increased nearly 90 times than that of ZVI alone. The effect of HA concentration on the degradation efficiency of PNP by ZVI was also discussed. The concentrations of Fe(Ⅱ) and Fe(Ⅲ) in reaction solution and on ZVI surface during the processes were measured. X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and transmission electron microscopy (TEM) of fresh and used ZVI were characterized, which elucidated that HA could facilitate the reduction of Fe(Ⅲ) to Fe(Ⅱ), retard passivation, and extend the pH range of reaction. The mechanism of high degradation efficient in ZVI/HA system was studied through a series of probing experiments. Fe0 directly donated electron to reduce PNP, which was the fundamental reason. The contribution of Fe(Ⅱ) and active hydrogen generated on ZVI surface to the degradation efficiency of PNP could be negligible. It can be concluded that the addition of HA was an effective strategy to improve the reduction efficiency of ZVI.

Green synthesis of zero valent iron using tannins to activate persulfate for sulfamethoxazole degradation

Majority zero-valent iron (ZVI) materials are prepared by reducing agents in liquid phase, resulting in the high environmental pollution and poor particle size distribution uniformity. Therefore, this study employed a green synthesis method to prepare ZVI. Tannins (TA) with phenolic hydroxyl groups that are characterized by strong reducing capacity were employed to synthesize ZVI (TA@ZVI). The dispersity and stability of ZVI was improved by TA, which inhibited the agglomeration of ZVI. Meanwhile, the specific surface area of TA@ZVI was higher than chemical prepared ZVI, increasing the reactive sites. The organic matter components enriched on TA could promote the adsorption of pollutants and complex with Fe(II/III) to enhance the reactivity of TA@ZVI. Also, the polyphenol structure in TA was oxidized to quinone, which facilitated electron transport. In order further test the performance of TA@ZVI, SMX was chosen as a target pollutant to study the oxidative degradation performance of TA@ZVI. SO4•− degraded about 16.4%–25.5% SMX and •OH degraded about 49.8%–63.9% SMX in the pH range of 4–6 while •OH played a dominant role in the neutral and alkaline conditions. Moreover, the presence of TA reduced Fe(III) to Fe(II) and promoted the release of Fe(II), providing a continuous source of •OH for the oxidative degradation of SMX. Besides, the conversion of Fe(II/III) was accelerated due to TA, which delayed the formation of passivation layer. Thus, TA enhanced the antioxidant capacity of ZVI. Generally, this study provided an environmental-friendly technology to synthesize and improve the reactivity of ZVI.

Oxalated zero valent iron enables highly efficient heterogeneous Fenton reaction by self-adapting pH and accelerating proton cycle

Heterogeneous Fenton reactions of zero-valent iron (ZVI) requires the sufficient release of Fe(II) to catalyze the H2O2 decomposition. However, the rate-limiting step of proton transfer through the passivation layer of ZVI restricted the Fe(II) release via Fe0 core corrosion. Herein we modified the shell of ZVI with highly proton-conductive FeC2O4·2H2O by ball-milling (OA-ZVIbm), and demonstrated its high heterogeneous Fenton performance of thiamphenicol (TAP) removal, with 500 times enhancement of the rate constant. More importantly, the OA-ZVIbm/H2O2 showed little attenuation of the Fenton activity during 13 successive cycles, and was applicable across a wide pH range of 3.5–9.5. Interestingly, the OA-ZVIbm/H2O2 reaction showed pH self-adapting ability, which initially reduced and then sustained the solution pH in the range of 3.5–5.2. The abundant intrinsic surface Fe(II) of OA-ZVIbm (45.54% vs. 27.52% in ZVIbm, according to Fe 2p XPS profiles) was oxidized by H2O2 and hydrolyzed to generate protons, and the FeC2O4·2H2O shell favored the fast transfer of protons to inner Fe0, therefore, the consumption-regeneration cycle of protons were accelerated to drove the production of Fe(II) for Fenton reactions, demonstrated by the more prominent H2 evolution and nearly 100% H2O2 decomposition by OA-ZVIbm. Furthermore, the FeC2O4·2H2O shell was stable and slightly decreased from 1.9% to 1.7% after the Fenton reaction. This study clarified the significance of proton transfer on the reactivity of ZVI, and provided an efficient strategy to achieve the highly efficient and robust heterogeneous Fenton reaction of ZVI for pollution control.

Removal of Cr(VI) by hollow micron zero-valent iron in groundwater containing different ions: Mechanisms and mineralized products

The development of zero-valent iron in-situ reactive zone technology is restricted by the poor mobility and reactivity of zero-valent iron. Hence，hollow micron zero-valent iron (H-mZVI) was prepared through rapid liquid reduction and used to remove Cr(VI) from aqueous solution. Scanning electron microscopy confirmed that H-mZVI had a hollow structure, particle size of approximately 1 µm, and rough surface. X-ray diffraction indicated that H-mZVI was mainly composed of ZVI. Brunauer–Emmett–Teller results showed that H-mZVI had a large specific surface area (25.54 m2/g) and pore volume (0.12 cm3/g). The Cr(VI) removal efficiency of H-mZVI was 6.18 times that of solid micron zero-valent iron (S-mZVI), and the removal reaction conformed to first-order reaction kinetics. Electrochemical test results revealed that the electron transport efficiency was stronger, Fe2+ concentration in aqueous solution was larger, and the decrease in oxidation–reduction potential was more obvious in H-mZVI than in S-mZVI. Desorption experiment and X-ray photoelectron spectroscopy showed that H-mZVI removed Cr(VI) primarily through reduction and secondarily through adsorption. The effects of conventional ions and humic acid (HA) on Cr(VI) removal by H-mZVI were in the order of PO43->HA>NO3->CO32->HCO3->Cl-=Mg2+=Ca2+. The corrosion products and their proportions varied in the presence of different ions.

Encapsulation of zero valent iron nanoparticles in biodegradable amphiphilic janus particles for groundwater remediation

Reactive Zero Valent Iron (ZVI) nanoparticles have been widely explored for in situ ground water remediation to degrade both non-aqueous phase liquid (NAPL) and water-soluble contaminants. However, they usually suffer from rapid oxidation and severe agglomerations restricting their delivery at NAPL/water interface. Aim of this study was to encapsulate the ZVI nanoparticles (50 nm) in amphiphilic bicompartmental Janus particles (711 ± 11 nm) fabricated by EHDC (electrohydrodynamic co-jetting). The dual compartments were composed of PLA (polylactic acid) and a blend of PLA, PE (poly (hexamethylene 2,3-O-isopropylidenetartarate) and PAG (photo acid generator). Upon UV irradiation, PAG releases acid to unmask hydroxyl groups present in PE to make only PE compartment hydrophilic. The entrapped ZVI nanoparticles (20 w/w%; ∼99 % encapsulation efficiency) were observed to degrade both hydrophilic (methyl orange dye) and hydrophobic (trichloro ethylene) contaminants. UV treated Janus particles provided stable dispersion (dispersed up to 3 weeks in water), prolonged reactivity (∼24 days in contaminated water), and recyclability (recyclable up to 9 times) as compared to non-treated ones. In addition, the amphiphilic Janus particles demonstrated high transportability (>95%) through porous media (sand column) with very low attachment efficiency (0.07), making them a promising candidate to target contaminants at NAPL/water interface prevailed in groundwater.

Long-term performance evaluation of zero-valent iron amended permeable reactive barriers for groundwater remediation – A mechanistic approach

Permeable reactive barriers (PRBs) are used for groundwater remediation at contaminated sites worldwide. This technology has been efficient at appropriate sites for treating organic and inorganic contaminants using zero-valent iron (ZVI) as a reductant and as a reactive material. Continued development of the technology over the years suggests that a robust understanding of PRB performance and the mechanisms involved is still lacking. Conflicting information in the scientific literature downplays the critical role of ZVI corrosion in the remediation of various organic and inorganic pollutants. Additionally, there is a lack of information on how different mechanisms act in tandem to affect ZVI-groundwater systems through time. In this review paper, we describe the underlying mechanisms of PRB performance and remove isolated misconceptions. We discuss the primary mechanisms of ZVI transformation and aging in PRBs and the role of iron corrosion products. We review numerous sites to reinforce our understanding of the interactions between groundwater contaminants and ZVI and the authigenic minerals that form within PRBs. Our findings show that ZVI corrosion products and mineral precipitates play critical roles in the long-term performance of PRBs by influencing the reactivity of ZVI. Pore occlusion by mineral precipitates occurs at the influent side of PRBs and is enhanced by dissolved oxygen and groundwater rich in dissolved solids and high alkalinity, which negatively impacts hydraulic conductivity, allowing contaminants to potentially bypass the treatment zone. Further development of site characterization tools and models is needed to support effective PRB designs for groundwater remediation.

Removal of tetracycline by biochar-supported biogenetic sulfidated zero valent iron: Kinetics, pathways and mechanism

The application of zero-valent iron (ZVI) is limited due to passivation and agglomeration. Therefore, biochar loading (MB) and biogenetic sulfidation via sulfate-reducing bacteria (SRB) were used to improve the reactivity of ZVI (BS-ZVI@MB) towards tetracycline (TC) degradation. Biochar provided more attachment sites for ZVI and SRB, thus alleviating the agglomeration. Additionally, quinone groups on biochar enhanced the electrons transfer through the measurement of electron donating/accepting capacities, and biogenetic sulfidation could inhibit the surface passivation of ZVI. Fe(Ⅱ/Ⅲ) produced after the addition of BS-ZVI@MB could complex with the A ring in TC to form Fe(Ⅱ/Ⅲ)-TC, which brought the oxidation of TC by complexed Fe(Ⅲ). Reactive oxygen species (ROS)(primarily •OH) were generated during the oxidation of Fe(Ⅱ), so as to promote the TC degradation. Extracellular polymeric substances (EPS) secreted from SRB had a slight quenching effect on ROS. Meanwhile, EPS formed a protective layer with Fe(Ⅱ/Ⅲ) on BS-ZVI@MB, reducing its reactivity with TC. Overall, this study showed an efficient modification technology of ZVI by biogenetic sulfidation and biochar loading for TC degradation.

Strategies to enhance the reactivity of zero-valent iron for environmental remediation: A review.

Application of zero-valent iron (ZVI) has become one of the most promising innovative technologies for the remediation of environmental pollutants. However, ZVI may suffer from the low intrinsic reactivity toward refractory pollutants, which seriously restricts its practical application in fields. Therefore, strategies have been developing to enhance the reactivity of ZVI. Until now, the most commonly used strategies include pretreatment of ZVI, synthesis of highly-active ZVI-based materials and additional auxiliary measures. In this review, a systematic and comprehensive summary of these commonly used strategies has been conducted for the following purposes: (1) to understand the fundamental mechanisms of the selected approaches; (2) to point out their advantages and shortcomings; (3) to illustrate the main problems of their large-scale application; (4) to forecast the future trend of developing ZVI technologies. Overall, this review is devoted to providing a fundamental understanding on the mechanism for enhancing the reactivity of ZVI and facilitating the practical application of ZVI technologies in fields.

Improved Electron Efficiency of Zero-Valent Iron towards Cr(VI) Reduction after Sequestering in Al2O3 Microspheres.

Zero-valent iron (ZVI) is widely used for groundwater remediation, but suffers from high electron consumption because of its free contact with non-target substrates such as O2. Here, ZVI-ALOX particles were prepared via in situ NaBH4 aqueous-phase reduction of ferrous ions (Fe2+) preabsorbed into Al2O3 microspheres. The electron efficiency (EE) and long-term performance of the material were improved by sequestering ZVI in the interspace of the Al2O3 microspheres (ZVI-ALOX). During long-term (350 days) continuous flow, Cr(VI) was removed to below the detection limit for over 23 days. Based on the high reactivity of ZVI towards Cr(VI), the EE of ZVI-ALOX was evaluated by measuring its Cr(VI) removal efficiency at neutral pH and comparing it with that of ZVI. The results showed that the EE of ZVI-ALOX during long-term continuous flow could reach 39.1%, which was much higher than that of ZVI (8.68%). The long-term continuous flow results also demonstrated that treatment of the influent solution achieved higher EE values than in the batch mode, where the presence of dissolved oxygen reduced EE values. At lower pollutant concentrations, the sequestering of ZVI was beneficial to its performance and long-term utility. In addition, measurement of the acute toxicity of treated column effluent using the indicator organism Photobacterium phosphoreum T3 showed that ZVI-ALOX could reduce the toxicity of 5 mg/L Cr(VI) solution by ~70% in 350 d. The results from this study provide a basis for the development of permeable reactive barriers for groundwater remediation based on sequestered ZVI.

Wet Milling of Zerovalent Iron in Sulfide Solution: Preserving and Securing the Metallic Iron

Herein, a critical problem regarding the milling of zerovalent iron (ZVI) to produce fine ZVI particles is solved. During milling, ZVI is prone to be rapidly oxidized by oxygen, water, and other potential oxidants in the milling environment, which results in significant metallic iron (Fe(0)) loss and raises safety concerns. In this work, a sulfide solution (using Na2S) is introduced as the milling solvent; as benchmarks, ZVI milling under a pure aqueous solution (ZVI(W)) and organic solvents (pure ethanol, ZVI(E)) is also investigated. Produced ZVIs are characterized with six different techniques to assess their Fe(0) content, safety, reactivity, and reductive capacity. The obtained results show that the sulfide solution is effective in minimizing Fe(0) oxidation during milling; the Fe(0) content (∼63%, w/w) of ZVI milled in sulfide solution (ZVI(S)) is more than 10 times that of ZVI(W) after 5 h of milling. ZVI(S) is comparable to ZVI(E) in their Fe(0) contents, reductive reactivity, and capacity, but ZVI(S) is more stable and safer in use; an optimal Na2S concentration of 10 g Na2S/L is recommended. A mechanistic study shows that Fe(0) preservation in a sulfide solution results from a combined effect of the alkaline pH of the solution and the coating of iron sulfides on ZVI. This exploratory study demonstrates an original milling solution for a highly scalable, economical, and safe scheme to produce ultrafine and reactive ZVI with a high Fe(0) content for environmental applications.

Enhanced reductive reactivity of zero-valent iron (ZVI) for pollutant removal by natural organic matters (NOMs) under aerobic conditions: Correlation between NOM properties and ZVI activity

While ubiquitous natural organic matters (NOMs) are capable of enhancing zero-valent iron (ZVI) performance under aerobic conditions, there is limited understanding of how the properties of NOMs affect the reactivity of ZVI towards contaminants removal. Here, the corresponding activity of ZVI under aerobic conditions was investigated in the presence of humic acid (HA), fulvic acid (FA), bovine serum albumin (BSA). It was found that three models of NOMs were all effective in promoting diatrizoate (DTA) reduction via depassivating ZVI. Interestingly, fast adsorption of NOM onto ZVI surface initially caused inconspicuous impact or visible inhibition on hydrophilic DTA reduction depending on their hydrophobicity. However, subsequent exposure of more reactive sites with high hydrophilicity arising from the detachment of surfaced NOM-associated iron oxide finally contributed to the enhanced consumption of Fe0 with the ability: HA > FA ≈ BSA, and 1-2 times increase in DTA removal kinetic rate following the order: HA > FA > BSA. It further revealed that there were two key factors in determining DTA removal under aerobic conditions, including the ability of NOMs to boost Fe0 consumption as contributed by their aromaticity degree and amino groups, and the hydrophobicity of NOMs to initially affect the property of ZVI surfaces.

Relevant design parameters for a reactor used in P removal with ZVI-based materials

Phosphate (P) retention onto zero valent iron (ZVI) particles and on iron oxyhydroxides has been widely investigated as a treatment process for domestic wastewater. Since such a process is less expensive and requires less maintenance than typical biological and physicochemical methods, it could provide a viable path to reaching high P removal capacities. This manuscript provides up-to-date information on P retention mechanisms, with the main ones being adsorption, precipitation and co-precipitation. The major experimental parameters affecting these mechanisms and ZVI reactivity are summarized. Through a review of batch studies and continuous reactor experiments, the P retention capacities of ZVI-based materials have been collated and compared according to test operating conditions, such as pH, initial adsorbate concentrations or hydrodynamic conditions. ZVI and its byproducts have already demonstrated high P retention capacities (up to 264 mg P/g ZVI). Methodological recommendations are provided to design reactor for phosphorus removal in wastewater treatment plants.

Anaerobic Corrosion of Zero-Valent Iron at Elevated Temperatures.

Increasing groundwater temperatures caused by global warming, subsurface infrastructure, or heat storage projects may interfere with groundwater remediation techniques using zero-valent iron (ZVI) technology by accelerating anaerobic corrosion. The corrosion behavior of three ZVIs widely used in permeable reactive barriers (PRBs), Peerless cast iron (PL), Gotthart-Maier cast iron (GM), and an ISPAT iron sponge (IS), was investigated at temperatures between 25 and 70 °C in half-open batch reactors by measuring the volume of hydrogen gas generated. Initially, the corrosion rates of all tested ZVIs increased with temperature; at temperatures ≤40 °C, a material-specific steady state is reached, and at temperatures >40 °C, passivation causes a decrease in long-term corrosion rates. The observed corrosion behavior was therefore assumed to be superimposed by accelerating and inhibiting effects, caused by surface precipitates where the fitting of measured corrosion rates by a modeling approach, using the corroded amount of Fe0 to account for passivating minerals, yields intrinsic activation energies (Ea, ZVI) of 81, 90, and 107 kJ mol-1 for IS, GM, and PL, respectively. An increase in H2 production might not be directly transferable to an increase in general ZVI reactivity; however, the results suggest that an increase in chlorinated hydrocarbon degradation rates can be expected for ZVI-PRBs in the immediate vicinity of low-temperature underground thermal energy storages (UTESs) or in the impact areas of high-temperature UTES with temperatures of ≤40 °C.

Improved performance and applicability of copper-iron bimetal by sulfidation for Cr(VI) removal

The reactivity of zero-valent iron (ZVI) for the Cr(VI) removal in groundwater is mainly limited by the formation of a passivation layer during its application in permeable reactive barrier (PRB). A kind of sulfidated copper-iron bimetal (S-ZVICu) with high reactivity for Cr(VI) removal was prepared by depositing FeSx onto copper modified ZVI via a one-pot method. The surface characteristic, reactivity and Cr(VI) removal performance of S-ZVICu were investigated. It was found that S-ZVICu had a Cr(VI) removal capacity as high as 67.5 mg/g and little risk of secondary contaminant of Cu(II). The optimal Cu/Fe mass ratio and S/Fe molar ratio were 0.0125 and 0.084, respectively. The S-ZVICu exhibited great superiority of Cr(VI) removal compared with ZVI, sulfidated ZVI (SZVI) and coper-iron bimetal (ZVICu). Mineralogy and morphology analysis showed that S-ZVICu had a hierarchical structure of Fe0/Cu0/FeSx, which could effectively reduce the risk of secondary contaminant of copper ions. The mechanism analysis suggested that the copper and FeSx successively plated on the surface of ZVI played a dual role in promoting the corrosion of zero-valent iron, and was facilitated to electron transfer between Fe0, Cu0, FeSx and Cr(VI). In addition, the loose FeSx layer had a positive effect on alleviating the oxidation of ZVI in air, which was helpful in maintaining the reactivity of S-ZVICu in the air. S-ZVICu is an environmentally friendly material for sustainable and effective removal of Cr(VI) in groundwater.

Effect of Copresence of Zerovalent Iron and Sulfate Reducing Bacteria on Reductive Dechlorination of Trichloroethylene.

Sulfur amendment of zerovalent iron (ZVI) materials has been shown to improve the reactivity and selectivity of ZVI toward a select group of organohalide contaminants in groundwater, most notably trichloroethene (TCE). In previous studies, chemical or mechanochemical sulfidation methods were used; however, the potential of using sulfate-reducing bacteria (SRB) to enable sulfur amendment has not been closely examined. In this study, lab-synthesized nanoscale ZVI (nZVI) and Peerless iron particles (ZVIPLS) were treated in a sulfate-reducing monoculture (D. desulfuricans) and an enrichment culture derived from freshwater sediments (AMR-1) prior to reactivity assessments with TCE as the model contaminant. ZVI conditioned in both cultures exhibited higher dechlorination efficiencies compared to unamended ZVIs. Remarkably, nZVI and ZVIPLS exposed to AMR-1 attained similar TCE dechlorination rates as their counterparts receiving chemical sulfidation (i.e., S-nZVI) using previously reported method. Product distribution data show that, in the SRB-ZVI system, abiotic dechlorination is the dominant TCE reduction pathway. In addition to dissolved sulfide, biogenic or synthesized FeS particles can enhance nZVI reactivity even as nZVI and FeS were not in direct contact, implying that SRB may influence the reactivity of ZVI via multiple mechanisms in different remediation situations. A shift in Archaea abundance in AMR-1 with nZVI amendment was observed but not with ZVIPLS. Overall, the synergy exhibited in the SRB-ZVI system may offer a valuable remediation strategy to overcome limitations of standalone biological or abiotic dechlorination approaches for chlorinated solvent abatement.