The profound review of Fenton process: What's the next step?

Fenton and Fenton-like processes, which could produce highly reactive species to degrade organic contaminants, have been widely used in the field of wastewater treatment. Therein, the chemistry of Fenton process including the nature of active oxidants, the complicated reactions involved, and the behind reason for its strongly pH-dependent performance, is the basis for the application of Fenton and Fenton-like processes in wastewater treatment. Nevertheless, the conflicting views still exist about the mechanism of the Fenton process. For instance, reaching a unanimous consensus on the nature of active oxidants (hydroxyl radical or tetravalent iron) in this process remains challenging. This review comprehensively examined the mechanism of the Fenton process including the debate on the nature of active oxidants, reactions involved in the Fenton process, and the behind reason for the pH-dependent degradation of contaminants in the Fenton process. Then, we summarized several strategies that promote the Fe(II)/Fe(III) cycle, reduce the competitive consumption of active oxidants by side reactions, and replace the Fenton reagent, thus improving the performance of the Fenton process. Furthermore, advances for the future were proposed including the demand for the high-accuracy identification of active oxidants and taking advantages of the characteristic of target contaminants during the degradation of contaminants by the Fenton process.

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.

Neutral Phenolic Contaminants Are Not Necessarily More Resistant to Permanganate Oxidation Than Their Dissociated Counterparts: Importance of Proton-Coupled Electron Transfer.

Despite decades of research on phenols oxidation by permanganate, there are still considerable uncertainties regarding the mechanisms accounting for the unexpected parabolic pH-dependent oxidation rate. Herein, the pH effect on phenols oxidation was reinvestigated experimentally and theoretically by highlighting the previously unappreciated proton transfer. The results revealed that the oxidation of protonated phenols occurred via proton-coupled electron transfer (PCET) pathways, which can switch from ETPT (electron transfer followed by proton transfer) to CEPT (concerted electron-proton transfer) or PTET (proton transfer followed by electron transfer) with an increase in pH. A PCET-based model was thus established, and it could fit the kinetic data of phenols oxidation by permanganate well. In contrast with what was previously thought, both the simulating results and the density functional theory calculation indicated the rate of CEPT reaction of protonated phenols with OH- as the proton acceptor was much higher than that of deprotonated phenols, which could account for the pH-rate profiles for phenols oxidation. Analysis of the quantitative structure-activity relationships among the modeled rate constants, Hammett constants, and pKa values of phenols further supports the idea that the oxidation of protonated phenols is dominated by PCET. This study improves our understanding of permanganate oxidation and suggests a new pattern of reactivity that may be applicable to other systems.

Unraveling the intrinsic mechanism behind the selective oxidation of sulfonamide antibiotics in the Mn(II)/periodate process: The overlooked surface-mediated electron transfer process.

Mn(II) exhibits a superb ability in activating periodate (PI) for the efficient degradation of aqueous organic contaminants. Nevertheless, ambiguous conclusions regarding the involved reactive species contributing to the removal of organic contaminants remain unresolved. In this work, we found that the Mn(II)/PI process showed outstanding and selective reactivity for oxidizing sulfonamides with the removal ranging from 57.1% to 100% at pH 6.5. Many lines of evidence suggest that the in-situ formed colloidal MnO2 (cMnO2) served as a catalyst to mediate electron transfer from sulfonamides to PI on its surface via forming cMnO2-PI complex (cMnO2-PI*) for the efficient oxidation of sulfonamides in the Mn(II)/PI process. Experimental results and density functional theory (DFT) calculations verify that the inclusive aniline moiety was the key site determining the electron transfer-dominated oxidation of sulfonamides. Furthermore, DFT calculation results reveal that the discrepancies in the removal of sulfonamides in the Mn(II)/PI process were attributed to different kinetic stability and chemical reactivity of sulfonamides caused by their heterocyclic substituents. In addition, a high utilization efficiency of PI was achieved in the Mn(II)/PI process owing to the surface-mediated electron transfer mechanism. This work provides deep insights into the surface-promoted mechanism in the cMnO2-involved oxidation processes.

Enhanced immobilization of lead, cadmium, and arsenic in smelter-contaminated soil by sulfidated zero-valent iron.

Soils contaminated with multiple heavy metal(loid)s (HMs) such as lead (Pb), cadmium (Cd), and arsenic (As) are of great concern in many countries. In this study, taking three lead-zinc smelter soils, the performance of sulfidated zero-valent iron (S-ZVI) toward Pb, Cd, and As immobilization was systemically investigated. Results showed that more than 88% of water-extractable Pb and Cd could be immobilized and transformed into reducible, oxidizable, and/or reducible forms by S-ZVI within 3 h, whereas only 3-56% of them could be immobilized by unsulfidated ZVI even after 72 h. Meanwhile, the phytoavailability of the tested HMs could be effectively reduced by 79% after S-ZVI amendment. More importantly, anoxic/oxic incubation tests revealed that the dissolved concentrations of HMs were much lower in S-ZVI-treated soils than in the untreated or unmodified ZVI-treated soils. Speciation analysis further suggested that unmodified ZVI seemed to reduce the long-term soil stability by changing the residual HMs species to mild-acid soluble and/or reducible ones. In contrast, S-ZVI could effectively alleviate the remobilization of HMs under the changeover of soil redox environments. All these findings indicate that S-ZVI may be a promising amendment for the immobilization of Pb, Cd, and As in smelter-contaminated soil.

Roles of MnO2 Colloids and Mn(III) during the Oxidation of Organic Contaminants by Permanganate.

Although intermediate manganese species can be generated during the reactions of permanganate (Mn(VII)) with organic pollutants in water, the role of the in situ generated MnO2 colloids in the Mn(VII) oxidation process remained controversial and the contribution of Mn(III) was largely neglected. This study showed that the apparent second-order rate constants (kapp) of Mn(VII) oxidation of methyl phenyl sulfoxide and carbamazepine remained constant with time. However, the degradation of four selected phenolic contaminants by Mn(VII) exhibited an autoaccelerating trend and a linear trend at pH 3.0-6.0 and pH 7.0-9.0, respectively. Multiple lines of evidence revealed that the occurrence of the autoaccelerating trend in the Mn(VII) oxidation process was ascribed to the oxidation of the phenolic organics by MnO2 colloids. The influence of pyrophosphate on the oxidation of different organic contaminants by MnO2 colloids suggests that Mn(III) was also responsible for the autoaccelerating oxidation of organic contaminants by Mn(VII) under specific reaction conditions. The kinetic models revealed that the overall contributions of MnO2 colloids and Mn(III) ranged within 6.6-67.9% during the autoaccelerating oxidation of phenolic contaminants by Mn(VII). These findings advance the understanding of the roles of MnO2 colloids and Mn(III) in the Mn(VII) oxidation process.

Mechanistic Insights into the Markedly Decreased Oxidation Capacity of the Fe(II)/S2O82- Process with Increasing pH.

The poor oxidation capacity of the Fe(II)/S2O82- [Fe(II)/PDS] system at pH > 3.0 has limited its wide application in water treatment. To unravel the underlying mechanism, this study systematically evaluated the possible influencing factors over the pH range of 1.0-8.0 and developed a mathematical model to quantify these effects. Results showed that ∼82% of the generated Fe(IV) could be used for pollutant degradation at pH 1.0, whereas negligible Fe(IV) contribution was observed at pH 7.5. This dramatic decline of Fe(IV) contribution with increasing pH dominantly accounted for the pH-dependent performance of the Fe(II)/PDS process. Unexpectedly, Fe(II) could consume ∼80% of the generated SO4•- non-productively under both acidic and near-neutral conditions, while the larger formation of Fe(III) precipitates at high pH inhibited the SO4•- contribution mildly. Moreover, the strong Fe(II) scavenging effect was difficult to be compensated for by slowing down the Fe(II) dosing rate. The competition of dissolved oxygen with PDS for Fe(II) was insignificant at pH ≤ 7.5, where the second-order rate constants for reactions of Fe(II) with oxygen were much lower than or comparable to that between Fe(II) and PDS. These findings could advance our understanding of the chemistry and application of the Fe(II)/PDS process.

[Investigation of the Performance of Organic Contaminant Degradation by Fe2+/PDS Under Environmentally Relevant pH Conditions].

Peroxydisulfate (PDS) activation by Fe2+ has proven to be a promising method to abate emerging organic contaminants by generating reactive oxidation species. Nevertheless, this process may only achieve good decontamination performance under acidic conditions, which has markedly limited its application in real practice. To address this issue, we comprehensively investigated the performance of the Fe2+/PDS process toward some probe contaminants at different pH levels and explored the potential change in reactive oxidative species and the influence of oxygen. Both SO4-· and Fe(Ⅳ) were identified to be involved in the Fe2+/PDS process, and the types of these oxidative species did not change with varying pH values. Although dissolved oxygen could compete with PDS for Fe2+, especially at high pH values, this competition process was not the major reason for the declined performance of the Fe2+/PDS process, since 37.6%-100% of PDS could also be activated with the presence of oxygen. Instead, the overdosing of Fe2+could greatly inhibit carbamazepine removal, indicating that the nonproductive consumption of reactive oxidants by Fe2+should account for the declined performance of Fe2+/PDS under environmentally relevant pH conditions. Accordingly, the feasibility of applying zero-valent iron and sulfidated zero-valent iron was further evaluated, and the formation of corrosion products was characterized using X-ray absorption fine structure spectroscopy. All these findings will improve our understanding about the Fe2+/PDS process and thus facilitate its application.

Understanding the Importance of Periodate Species in the pH-Dependent Degradation of Organic Contaminants in the H2O2/Periodate Process.

Although periodate-based advanced oxidation processes have been proven to be efficient in abating organic contaminants, the activation properties of different periodate species remain largely unclear. Herein, by highlighting the role of H4IO6-, we reinvestigated the pH effect on the decontamination performance of the H2O2/periodate process. Results revealed that elevating pH from 2.0 to 10.0 could markedly accelerate the rates of organic contaminant decay but decrease the amounts of organic contaminant removal. This pH-dependent trend of organic contaminant degradation corresponded well with the HO· yield and the variation of periodate species. Specifically, although 1O2 could be detected at pH 9.0, HO· was determined to be the major reactive oxidizing species in the H2O2/periodate process under all the tested pH levels. Furthermore, it was suggested that only H4IO6- and H2I2O104- could serve as the precursors of HO·. The second-order rate constant for the reaction of H2I2O104- species with H2O2 was determined to be ∼1199.5 M-1 s-1 at pH 9.0, which was two orders of magnitude greater than that of H4IO6- (∼2.2 M-1 s-1 at pH 3.0). Taken together, the reaction pathways of H2O2 with different periodate species were proposed. These fundamental findings could improve our understanding of the periodate-based advanced oxidation processes.

A novel design of in-line static mixer for permanganate/bisulfite process: Numerical simulations and pilot-scale testing.

An increasing number of chemical technologies to wipe out contaminants within an incredibly short period of time have been developed recently, while their application was always hindered by the inefficient or improper mixing of reactants. To address this issue, the present work proposed a new static mixer named Tai-Chi which consists of blade, fin, and spoiler elements. Tai-Chi mixer can slice and divert the solutions inside and generate high shear flow to promote mixing process. Numerical simulations helped to determine the optimal operating conditions for Tai-Chi mixer, including laying its components anterior to the injection nozzles and keeping the velocity rate ratio of main pipe to branch pipe within the range of 0.5 to 1. Numerical simulations further proved that Tai-Chi mixer could strike a great balance between mixing performance (coefficient of variation [CoV] reaches 0.1 within 5 to 7 pipe diameters downstream) and head loss (nearly a half of other high shear static mixer in the market). Data of pilot-scale testing by Tai-Chi mixer confirm that 80% sulfamethoxazole could be eliminated in permanganate/bisulfite process within 8 pipe diameters, as well as showed the superiority of Tai-Chi's mixing performance in early stage compared with other static mixers in the market. PRACTITIONER POINTS: A Tai-Chi static mixer with blade, fin, and spoiler elements is devised. The optimal condition of flow rate and installment of Tai-Chi mixer is determined. Ultra-fast mixing is achieved by Tai-Chi (CoV < 0.1 within 5-7 pipe diameters). Pilot-scale test verifies the mixing efficiency of Tai-Chi mixer.

Simultaneous Sequestration of Humic Acid-Complexed Pb(II), Zn(II), Cd(II), and As(V) by Sulfidated Zero-Valent Iron: Performance and Stability of Sequestration Products.

Heavy metal(loid)s (HMs) such as Pb(II), Zn(II), Cd(II), and As(V) are ubiquitously present in co-contaminated soil and shallow groundwater, where the humic acid (HA)-rich environments can significantly influence their sequestration. In this study, sulfidated zero-valent iron (S-ZVI) was found to be able to simultaneously sequestrate these HA-complexed HMs. Specially, the HA-complexed Pb(II), Zn(II), Cd(II), and As(V) could be completely removed by S-ZVI within 60 min, while only 35-50% of them could be sequestrated within 72 h by unsulfidated ZVI. Interestingly, different from the S-ZVI corrosion behavior, the kinetics of HM sequestration by S-ZVI consisted of an initial slow reaction stage (or a lag phase) and then a fairly rapid reaction process. Characterization results indicated that forming metal sulfides controlled the HM sequestration at the first stage, whereas the enhanced ZVI corrosion and thus-improved adsorption and/or coprecipitation by iron hydroxides governed the second stage. Both metal-oxygen and metal-sulfur bonds in the solid phase could be confirmed by X-ray photoelectron spectroscopy and extended X-ray absorption fine structure analysis. Moreover, the transformation of S species from SO42-, SO32-, and S22- to S2- under reducing conditions could allow the sequestrated HMs to remain stable over a long period.

Abiotic reductive removal of organic contaminants catalyzed by carbon materials: A short review.

Since the observation that carbon materials can facilitate electron transfer between reactants, there is growing literature on the abiotic reductive removal of organic contaminants catalyzed by them. Most of the interest in these processes arises from the participation of carbon materials in the natural transformation of contaminants and the possibility of developing new strategies for environmental treatment and remediation. The combinations of various carbon materials and reductants have been investigated for the reduction of nitro-organic compounds, halogenated organics, and azo dyes. The reduction rates of a certain compound in carbon-reductant systems vary with the surface properties of carbon materials, although there are controversial conclusions on the properties governing the catalytic performance. This review scrutinizes the contributions of quinone moieties, electron conductivity, and other carbon properties to the activity of carbon materials. It also discusses the contaminant-dependent reduction pathways, that is, electron transfer through conductive carbon and intermediates formed during the reaction, along with possibly additional activation of contaminant molecules by carbon. Moreover, modification strategies to improve the catalytic activity for reduction are summarized. Future research needs are proposed to advance the understanding of reaction mechanisms and improve the practical utility of carbon material for water treatment. PRACTITIONER POINTS: Reduction rates of contaminants in carbon-reductant systems and modification strategies for carbon materials are summarized. Mechanisms for the catalytic activity of carbon materials are discussed. Research needs for new insights into carbon-catalyzed reduction are proposed.

Enhanced Oxidation of Organic Contaminants by Mn(VII)/CaSO3 Under Environmentally Relevant Conditions: Performance and Mechanisms.

Although permanganate activation by sodium sulfite (Mn(VII)/Na2SO3) has shown great potential for rapid abatement of organic contaminants, the limited reactivity under alkaline conditions and undesirable Mn residual may prevent its widespread application. To solve these challenges, calcium sulfite (CaSO3) was employed as a slow-release source of SO32-/HSO3- (S(IV)) to activate Mn(VII) in this study. It was found that the application of CaSO3 solid could extend the effective working pH range of Mn(VII)/S(IV) from ≤7.0 to ≤9.0. Moreover, due to the enhanced precipitation of MnO2 with the presence of Ca2+, very low Mn residual (<0.05 mg/L) was achieved in Mn(VII)/CaSO3 system. Mn(VII)/CaSO3 system is a unique two-stage oxidation process in terms of reaction kinetics and reactive oxidants. Specifically, Mn(VII) was rapidly consumed and reactive Mn intermediates (e.g., Mn(VI), Mn(V)), SO4•-, and HO• were produced in the first stage. However, the second stage was governed by the interaction between MnO2 and S(IV), with SO4•- and HO• serving as the dominant reactive oxidants. Taking advantage of an automatic titrator, excess S(IV) was found to greatly quench the generated radicals, whereas it did not cause a significant consumption of reactive Mn species. All these results improved our understanding of the Mn(VII)/S(IV) process and could thus facilitate its application.

Trace organic contaminants abatement by permanganate/bisulfite pretreatment coupled with conventional water treatment processes: Lab- and pilot-scale tests.

Bisulfite-activated permanganate (PM/BS) process has proven to be a promising method for trace organic contaminants (TrOCs) abatement. However, to our knowledge, most previous studies on PM/BS process were limited in synthetic water at lab-scale. Hence, the performance of TrOCs abatement by PM/BS process was investigated in real waters in this study, and for the first time, its feasibility as a pretreatment process was evaluated at pilot-scale. The lab-scale results indicated that almost all tested TrOCs could be completely removed from pure water, while their removal efficiencies varied widely from ∼20 % to ∼90 % in real waters. Correlation analysis suggested that TrOCs abatement decreased linearly with increasing concentration of dissolved organic matter (DOM) and halide ions in real waters. The TrOCs with electron-donating groups were more likely to be decomposed in PM/BS process. The PM/BS pretreatment produced MnO2 and decreased the aromatic signal of the DOM, which enhanced the removal of DOM during subsequent coagulation-sedimentation processes. Comparing with ozonation, chlorination, and permanganate processes, PM/BS process showed some advantages in terms of TrOCs abatement and operating costs. Furthermore, the pilot-scale experiment confirmed that PM/BS process combined with traditional water treatment processes could achieve excellent TrOCs abatement (greater than 84%).

Weak magnetic field enables high selectivity of zerovalent iron toward metalloid oxyanions under aerobic conditions.

For water treatment/remediation by zerovalent iron (ZVI), of particular concern is its selectivity toward contaminants over natural non-targets (e.g., O2 and H2O/H+). Hence, the effects of weak magnetic field (WMF) on the selectivity of ZVI toward metalloid oxyanions (i.e., As(III), As(V), Sb(III), Sb(V), Se(IV) and Se(VI)) were in-depth investigated under aerobic conditions. This study unraveled that, despite the electron utilization (EU) of ZVI with and without WMF were almost identical at reaction equilibrium, the application of a WMF could enhance the specific removal capacity (SRC) of ZVI toward metalloid oxyanions from 1.8-19.0 mg/g Fe to 12.6-85.3 mg/g Fe. Particularly, the electron efficiency (EE) of ZVI with WMF for reduction of Se(IV)/Se(VI) were 3.7- to 14.1-fold greater than that without WMF. Since the WMF-induced magnetic gradient force (FΔB) can derive the movement of both Fe2+ and metalloid oxyanions, the subsequent incorporation of metalloid oxyanions with in-situ generated iron oxides can also been mediated synchronously and thus leading to an enhanced SRC of ZVI (also EE for Se(IV) and Se(VI) reduction by ZVI). In general, our findings prove that WMF should be a promising method to promote the selectivity of ZVI for water decontamination under aerobic conditions.

Enhanced trichloroethylene dechlorination by carbon-modified zero-valent iron: Revisiting the role of carbon additives.

Given that there are still some debates on the influence of carbon modification on zerovalent iron (ZVI) decontamination process, the roles of carbon on trichloroethylene (TCE) reduction by ZVI were re-investigated in this work. Compared to activated carbons (AC) with high adsorption ability, carbon fibers (CF) with good electronic conductivity performed much better in enhancing ZVI performance in terms of both reactivity and selectivity. Moreover, it was interesting to observe that a low carbon loading is sufficient to effectively improve TCE reduction and this promoting effect would decline with further increasing the carbon amounts from 1.0 wt.% to 50 wt.%. Regarding to the ZVI selectivity, a relatively high carbon loading (especially for CF, it may be as high as 50 wt.%) was needed to protect ZVI from non-productive reactions with H2O/H+ effectively. However, a mixture of 10 wt.% AC and 1.0 wt.% CF could combine their respective merits of inhibiting side reactions and enhancing TCE reduction, and thus simultaneously enhanced the reactivity and selectivity of ZVI. Mechanistic investigations revealed that carbon modification could enhance the ZVI performance through improving TCE adsorption and/or accelerating electron transfer, while the latter one may play a more important role especially at high carbon loadings.

Ferrous ion mitigates the negative effects of humic acid on removal of 4-nitrophenol by zerovalent iron.

In this study, Fe2+ addition was employed to overcome the negative effects of humic acid (HA) on contaminant removal by zerovalent iron (ZVI), and its feasibility to improve electron efficiency of ZVI was also tested. HA at high concentrations suppressed the removal of 4-nitrophenol (4-NP) by ZVI, while the addition of 0.25-1.0 mM Fe2+ could greatly mitigate this inhibitory effect and enhance 4-NP reduction. Specifically, with a mixed-order model, global fitting results showed that the addition of Fe2+ increased the rate constant from 0.124 × 10-2-0.219 × 10-2 mM/min to 0.227 × 10-2-0.417 × 10-2 mM/min and shortened lag period from 19.7-47.9 min to 8.0-15.2 min for 4-NP removal. The mechanistic investigation revealed this trend could be explained by the following aspects: i) Fe2+ can facilitate the generation of Fe(II)-containing oxides, which can act as an electron mediator or direct electron donor for 4-NP reduction; ii) the presence of Fe2+ could lead to aggregation of HA particles and accordingly reduced its coverage on ZVI surface. But the results of respike experiments indicate that Fe2+ addition did not show remarkable effect on the electron efficiency of 4-NP by ZVI, which should be associated with that Fe2+ was not able to favor the enrichment of 4-NP on ZVI surface.

Role of pyrophosphate on the degradation of sulfamethoxazole by permanganate combined with different reductants: Positive or negative.

Activating permanganate with reductants has gained increasing attention recently for efficient organic contaminants abatement via reactive intermediate Mn species. However, few studies have been conducted to explore the role of pyrophosphate (PP), a typical complexing agent for intermediate Mn species, in activated permanganate systems. In this study, taking sulfamethoxazole (SMX) as a probe compound, the influences of PP on SMX degradation by permanganate/thiosulfate and permanganate/hydroxylamine were extensively studied. It was found that both thiosulfate and hydroxylamine were able to activate permanganate for oxidation of SMX in the absence of PP. However, upon the introduction of PP, opposite effects were observed in the two systems where PP further improved the activation of permanganate by thiosulfate but dampened the performance of permanganate/hydroxylamine markedly. For permanganate/hydroxylamine system, MnO2 was determined to be the only reactive oxidative species accounting for SMX degradation in the absence of PP, and its generation could be completely inhibited by PP. While in permanganate/thiosulfate system, both Mn(V) and MnO2 were responsible for SMX oxidation, and the introduction of PP could strengthen the oxidative ability of Mn(V). These results could shed some insights on the suitability of applying PP to explore the kinetics and mechanisms of manganese involved redox reactions. PRACTITIONER POINTS: Both Na2 S2 O3 and NH2 OH·HCl can activate KMnO4 for SMX removal without PP. MnO2 is the reactive oxidative species involved in KMnO4 /NH2 OH·HCl system. Mn(V) and MnO2 account for the SMX oxidation by KMnO4 /Na2 S2 O3 system. PP could inhibit the formation of MnO2 but enhance the oxidative ability of Mn(V).

Coupled Effect of Sulfidation and Ferrous Dosing on Selenate Removal by Zerovalent Iron Under Aerobic Conditions.

Both the reactivity and the removal capacity of zerovalent iron (ZVI) for the target contaminant are important for applying ZVI in wastewater treatment. In this study, the feasibility of combining sulfidation treatment and Fe2+ dosing (S-ZVI/Fe2+) to enhance the performance of ZVI for Se(VI) removal was comprehensively investigated under aerobic conditions. Se(VI) was first adsorbed on the surface of ZVI particles and then reduced to Se(IV) and Se(0) with Se(0) being the final product in S-ZVI/Fe2+ system. This system bore the advantages of both sulfidation treatment (S-ZVI) and Fe2+ dosing (ZVI/Fe2+) for Se(VI) removal. The amounts and rate constants of Se(VI) removal in S-ZVI/Fe2+ system were increased by 1.8-32.8 times and 11.7-194.0 times, respectively, compared to those in pristine ZVI system. Sulfidation significantly accelerated the corrosion of Fe0 thus improved the removal rate of Se(VI). The promoting effect of Fe2+ on Se(VI) sequestration by S-ZVI should be mainly associated with the following facts: Fe2+ could maintain a relatively low pH level during Se(VI) removal by S-ZVI; Compared to S-ZVI alone, the consumption of Fe0 in S-ZVI/Fe2+ by O2/H+ was slower, and thus the electron efficiency of S-ZVI was elevated; Fe2+ dosing facilitated electron transfer by forming semiconductive Fe3O4.

Enhanced immobilization of chromium(VI) in soil using sulfidated zero-valent iron.

Batch tests were conducted in this study to evaluate the influence of sulfidation on the remediation of Cr(VI) in soil by zero-valent iron (ZVI). It was demonstrated that sulfidated ZVI synthesized by ball-milling with elemental sulfur (S-ZVIbm) could reduce and immobilize Cr(VI) in soil more rapidly and efficiently than unamended ZVI (ZVIbm). Specifically, with the optimal S/Fe molar ratio of 0.05 and ZVI dosage of 5 wt%, S-ZVIbm could completely sequestrate water soluble Cr(VI) (as high as 17.5 mg/L) within 3 h, while negligible Cr(VI) was reduced by ZVIbm over a 3-day incubation period under identical conditions. Furthermore, sequential extraction analysis revealed that S-ZVIbm treatment also promoted the conversion of exchangeable Cr to more stable forms (i.e., mainly as FeMn oxides bound fraction). XPS analysis showed that reduction was the main Cr(VI) remediation mechanism by ZVI, and alkaline extraction experiments further demonstrated Cr(VI) concentration in soil could be decreased from 153.6 mg/kg to 23.4 and 131.6 mg/kg by S-ZVIbm and ZVIbm, respectively. A magnetic separation process was introduced in this study to physically remove the residual ZVI particles and attached iron (hydr)oxides so as to minimize the re-release risk of immobilized Cr. Results revealed that, 71-89% of the added Fe and 9.5-33.6% of Cr could be retrieved from S-ZVIbm-treated soil. These findings highlighted the potential of S-ZVIbm as a promising amendment for immobilizing Cr(VI) in soil and the potential of magnetic separation as an alternative option for preventing the re-mobilization of sequestered Cr.