Sulfidated Nanoscale Zerovalent Iron Research Articles

Surface wettability control and electron transport regulation in zerovalent iron for enhanced removal of emerging polystyrene microplastics-heavy metal contaminants

Emerging microplastics-heavy metal (MPs-HM) contaminants in wastewaters pose an emerging health and environmental risk due to their persistence and increasing ecological risks (e.g., “Trojan horse” effect). Hence, removing MPs in solution and preventing secondary releases of HM has become a key challenge when tackling with MPs pollution. Leveraging the hydrophobic nature of MPs and the electron transfer efficiency from Fe0 to HM, we demonstrate an alkylated and sulfidated nanoscale zerovalent iron (AS-nZVI) featuring a delicate “core-shell-hydrophobic film” nanostructure. Exemplified by polystyrene (PS) MPs-Pb(II) removal, the three nanocomponents offer synergistic functions for the rapid separation of MPs, as well as the reduction and stabilization of Pb(II). The outmost hydrophobic film of AS-nZVI greatly improves the anticorrosion performance of nanoscale zerovalent iron and the enrichment abilities of hydrophobic MPs, achieving a maximum removal capacity of MPs to 2725.87 mgMPs·gFe−1. This MPs enrichment promotes the subsequent reductive removal of Pb(II) through the electron transfer from the iron core of AS-nZVI to Pb(II), a process further strengthened by the introduced sulfur. When considering the inevitable aging of MPs in wastewaters due to mechanical wear or microbial degradation, our study concurrently examines the efficiencies and behaviors of AS-nZVI in removing virgin-MPs-Pb(II) and aged-MPs-Pb(II). The batch results reveal that AS-nZVI has an exceptional ability to remove above 99.6 % Pb(II) for all reaction systems. Overall, this work marks a pioneering effort in highlighting the importance of MPs-toxin combinations in dealing with MPs contamination and in demonstrating the utility of nZVI techniques for MPs-contaminated water purification.

Evaluating the effectiveness of sulfidated nano zerovalent iron and sludge co-application for reducing metal mobility in contaminated soil

Sewage sludge has long been applied to soils as a fertilizer yet may be enriched with leachable metal(loid)s and other pollutants. Sulfidated nanoscale zerovalent iron (S-nZVI) has proven effective at metal sorption; however, risks associated with the use of engineered nanoparticles cannot be neglected. This study investigated the effects of the co-application of composted sewage sludge with S-nZVI for the stabilization of Cd, Pb, Fe, Zn. Five treatments (control, Fe grit, composted sludge, S-nZVI, composted sludge and S-nZVI), two leaching fluids; synthetic precipitation leaching procedure (SPLP) and toxicity characteristic leaching procedure (TCLP) fluid were used, samples were incubated at different time intervals of 1 week, 1, 3, and 6 months. Fe grit proved most efficient in reducing the concentration of extractable metals in the batch experiment; the mixture of composted sludge and S-nZVI was the most effective in reducing the leachability of metals in the column systems, while S-nZVI was the most efficient for reducing about 80% of Zn concentration in soil solution. Thus, the combination of two amendments, S-nZVI incorporated with composted sewage sludge and Fe grit proved most effective at reducing metal leaching and possibly lowering the associated risks. Future work should investigate the longer-term efficiency of this combination.

Carboxymethyl cellulose stabilization induced changes in particle characteristics and dechlorination efficiency of sulfidated nanoscale zero-valent iron

Polymer stabilization, exemplified by carboxymethyl cellulose (CMC), has demonstrated effectiveness in enhancing the transport of nanoscale zero-valent iron (nZVI). And, sulfidation is recognized for enhancing the reactivity and selectivity of nZVI in dechlorination processes. The influence of polymer stabilization on sulfidated nZVI (S-nZVI) with various sulfur precursors remains unclear. In this study, CMC-stabilized S-nZVI (CMC-S-nZVI) was synthesized using three distinct sulfur precursors (S2−, S2O42−, and S2O32−) through one-step approach. The antioxidant properties of CMC significantly elevated the concentration of reduced sulfur species (S2−) on CMC-S-nZVIs, marking a 3.1–7.0-fold increase compared to S-nZVIs. The rate of trichloroethylene degradation (km) by CMC-S-nZVIs was observed to be 2.2–9.0 times higher than that achieved by their non-stabilized counterparts. Among the three CMC-S-nZVIs, CMC-S-nZVINa2S exhibited the highest km. Interesting, while the electron efficiency of CMC-S-nZVIs surged by 7.9–12 times relative to nZVI, it experienced a reduction of 7.0–34% when compared with S-nZVIs. This phenomenon is attributed to the increased hydrophilicity of S-nZVI particles due to CMC stabilization, which inadvertently promotes the hydrogen evolution reaction (HER). In conclusion, the findings of this study underscores the impact of CMC stabilization on the properties and dechlorination performance of S-nZVI sulfidated using different sulfur precursors, offering guidance for engineering CMC-S-nZVIs with desirable properties for contaminated groundwater remediation.

Processes and mechanisms in remediation of aqueous chromium contamination by sulfidated nano-scale zerovalent iron (S-nZVI): Experimental and computational investigations

Sulfidated nano-scale zerovalent iron (S-nZVI) has emerged as an advanced functional nanomaterial for efficiently remediating Cr(VI) contamination in aqueous environments. However, there is an insufficient understanding of its coherent process, removal pathway, and hydrochemical reactive mechanisms, presenting potential challenges for its future environmental applications. To address this gap, this study successfully synthesized S-nZVI through a chemical precipitation method and effectively applied it for the removal of Cr(VI). Additional characterization revealed that the removal of Cr(VI) followed a sequence of rapid chemisorption and intraparticle diffusion processes, concomitant with an increase in pH and a decrease in oxidation-reduction potential. The remediation mechanism encompassed a synergistic reduction of Cr(VI) to Cr(III) and simultaneous immobilization via Cr2FeO4 coprecipitation. The highest Cr(VI) removal capacity of 75 mg/g was attained during dynamic removal experiments in the sand column packed with S-nZVI. Further computational analysis, employing density functional theory calculations based on the experimental data, revealed the involvement of multiple molecular orbitals of Cr(VI) in the removal process. It also elucidated a step-by-step reduction pathway for Cr(VI) characterized by decreasing free energy. These findings provide evidence-based insights into Cr(VI) remediation using S-nZVI and can serve as valuable technical support for future environmental management of heavy metals.

Dechlorination Helps Defluorination: Insights into the Defluorination Mechanism of Florfenicol by S-nZVI and DFT Calculations on the Reaction Pathways.

Defluorination is essential to eliminate the antibiotic resistance and detrimental effects of florfenicol (C12H14Cl2FNO4S, FF), which is achievable by sulfidated nanoscale zerovalent iron (S-nZVI), yet a comprehensive understanding of the mechanism is lacking. Herein, we used experimental data and density functional theory calculations to demonstrate four dechlorination-promoted defluorination pathways of FF, depending on S-nZVI or not. FF was defluorinated in a rapid and then slow but continuous manner, accompanying a consecutive dechlorination to deschloro (dFF) and dideschloro FF (ddFF). Unexpectedly, the predominant defluorination occurs by spontaneous hydrolysis of ddFF to form the hydrolyzed byproduct (HO-ddFF), i.e., independent of S-nZVI, which is initiated by intramolecular attack from carbonyl O to alkyl F and is thus limited for FF and dFF owing to the diminished nucleophilicity by electron-withdrawing Cl. The removal of Cl also makes the reductive defluorination of ddFF by S-nZVI amenable. The other two minor but more rapid defluorination pathways occur in synergy with the dechlorination of FF and dFF, which are mediated by the reactive carbanion intermediates and generate HO-dFF and HO-ddFF, respectively. The reliability of these dechlorination-facilitated defluorination pathways was verified by the consistency of theoretical calculations with experimental data, providing valuable insights into the degradation of fluorinated contaminants.

Unravelling the removal mechanisms of trivalent arsenic by sulfidated nanoscale zero-valent iron: The crucial role of reactive oxygen species and the multiple effects of citric acid

The remediation of arsenic-contaminated groundwater by sulfidated nanoscale zero-valent iron (S-nZVI) has raised considerable attention. However, the role of trivalent arsenic (As(III)) oxidation by S-nZVI in oxic conditions (S-nZVI/O2) remains controversial, and the comprehensive effect of citric acid (CA) prevalent in groundwater on As(III) removal by S-nZVI remains unclear. Herein, the mechanisms of reactive oxygen species (ROS) generation and multiple effects of CA on As(III) removal by S-nZVI/O2 were systematically explored. Results indicated that the removal efficiency of As(III) by S-nZVI/O2 (97.81 %) was prominently higher than that by S-nZVI (66.71 %), resulting from the significant production of ROS (mainly H2O2 and OH) under oxic conditions, which played a crucial role in promoting the As(III) oxidation. Additionally, CA had multiple effects on As(III) removal by S-nZVI/O2 system: (i) CA impeded the diffusion of As(III) towards S-nZVI and increased the secondary risk of immobilized As(III) re-releasing into the environment due to the Fe dissolution from S-nZVI; (ii) CA could significantly enhance the yields of OH from 25.29 to 133.00 μM via accelerating the redox cycle of Fe(II)/Fe(III) and increasing the oriented conversion rate of H2O2 to OH; (iii) CA could also enrich the types of ROS (such as O2− and 1O2) in favor of further As(III) oxidation. This study contributed novel findings regarding the control of As(III) contaminated groundwater using S-nZVI technologies.

Sulfidated nanoscale zero-valent iron derived from iron sludge for tetracycline removal: Role of sulfur and iron in reactivity and mechanisms

Iron sludge, produced during the drinking water treatment process, can be recycled as potential iron resource to create environmental functional material. In this study, sulfur-iron composites derived from iron sludge (S–Fe composites) was synthesized through sulfidation and carbonization, and used for the tetracycline (TC) removal under aerobic and anoxic conditions. The reactivities of these as-prepared products were strongly depended on pyrolysis temperatures. In particular, sulfidated nanoscale zero-valent iron loaded on carbon (S-nFe0@CIS) carbonized at 800 °C exhibited the highest TC removal efficiency with 86.6% within 30 min at circumneutral pH compared with other S–Fe composites. The crystalline structure of α-Fe0, FeSx and S0 as main active sites in S-nFe0@CIS promoted the degradation of TC. Moreover, the Fe/S molar ratios significantly affected the TC removal rates, which reached the best value as the optimal S/Fe of 0.27. The results illustrated that the optimized extent of sulfidation could facilitate electron transfer from nFe0 towards contaminants and accelerate Fe(III)/Fe(II) cycle in reaction system compared to bared nFe0@CIS. We revealed that removal of TC by S-nFe0@CIS in the presence of dissolved oxygen (DO) is mainly attributed to oxidation, adsorption and reduction pathways. Their contribution to TC removal were 31.6%, 25.2% and 28.8%, respectively. Furthermore, this adsorption-oxygenation with the formation of S-nFe0@CIS-TC* complexes was a surface-mediated process, in which DO was transformed by the structural FeSx on complex surface to •OH with the generation of H2O2 intermediate. The intermediates of TC and toxicity analysis indicate that less toxicity products generated through degradation process. This study provides a new reclamation of iron sludge and offers a new insight into the TC removal by S-nFe0@CIS under aerobic conditions.

Enhanced removal of aqueous arsenic(III) by sulfidated nanoscale zero-valent iron under oxic conditions: Performance and mechanism

Although sulfidated nanoscale zero-valent iron (S-nZVI) has shown significant promise in the removal of aqueous inorganic arsenic (As), there is a scarcity of studies comprehensively investigating their performance under oxic conditions, as well as the mechanism involving oxidation being elucidated. In this study, the synthesized S-nZVI exhibited a distinctive core-shell structure, characterized by an outer shell comprising iron oxides and FeS, while also demonstrating increased specific surface areas and decreased pHZPC value. Batch experiments revealed that sulfidation significantly enhanced the As(III) removal efficiency of nZVI under oxic conditions by increasing both the reaction rates and adsorption capacity (qm = 495.23 mg/g). Furthermore, several critical factors influencing the As(III) removal by S-nZVI were investigated, indicating that increased initial As(III) concentrations, initial pH values, and co-existing anions concentrations had negative impacts on the removal process; however, an increase in ionic strength showed certain positive effects. Based on the profiles of As and Fe, roles of reactive species, and characterization of reacted products, it could be concluded that As(III) removal by S-nZVI involves the synergistic effect of adsorption, co-precipitation, and oxidation. More importantly, sulfidation facilitated the corrosion of Fe0, accelerating the release of Fe2+ and promoting the activation of single-electron molecular oxygen reactions, thereby further enhancing the total As removal efficiency. This study highlights the excellent potential of S-nZVI for effectively removing As(III) under oxic conditions.

Performance and mechanisms of active attapulgite-supported sulfidated nanoscale zero-valent iron materials for Pb(II) removal from aqueous solution

To inhibit the oxidation, passivation, and agglomeration of nano-zero-valent iron (nZVI), a liquid phase reduction method was used to load sulfurized nZVI onto acid-modified ATP with attapulgite (ATP) as the carrier (S-nZVI@ATP). The performance and mechanism of this material were studied for Pb2+ removal in water. The S-nZVI@ATP preparation prevents the agglomeration of nZVI particles and reduces nZVI oxidation. Pb2+ removal proceeds efficiently and stably when using S-nZVI@ATP at pH values ranging from 2.5–5.5. According to the electron sharing and transfer-based pseudo-second-order kinetic model, the Pb2+ is adsorbed onto S-nZVI@ATP, and the speed control step is completed by liquid film diffusion and intraparticle diffusion. The S-nZVI@ATP mediated Pb2+ adsorption is well-described by Freundlich’s isothermal adsorption model, which is a multilayer chemical adsorption process. The temperature and initial Pb2+ concentration were varied, and it was determined that Pb2+ adsorbs on S-nZVI@ATP in an endothermic reaction. This S-nZVI@ATP composite material has high reducibility, high surface activity, and good adsorption properties for Pb2+. Tests were performed for 24 h using adsorbent (1 g l−1) in Pb2+ solution (30 ml). For an initial Pb2+ concentration of 700 mg l−1, S−1-nZVI@ATP removes 57.37% of the Pb2+ and has an adsorption capacity of 401.60 mg g−1. In addition to forming PbS and Pb(OH)2 precipitates, Pb2+ also complexes with the Fe/H oxide shell of S-nZVI@ATP, and Fe0 reduces some Pb2+ on the nZVI to Pb0. The results exhibited that S-nZVI@ATP has excellent potential as an adsorbent for the removal of Pb2+ from the industrial wastewater.

Long-term stability and toxicity effects of three-dimensional electrokinetic remediation on chromium-contaminated soils

The three-dimensional electrokinetic remediation (3D EKR) achieved efficient removal of chromium (Cr) from the soil through mechanisms including electromigration, electroosmosis, and redox reactions. In this study, the long-term stability, leaching toxicity, bioavailability, and phytotoxicity of Cr in remediated soils were systematically analyzed to comprehensively evaluate the effectiveness of the 3D EKR method. The results showed that the concentration of hexavalent chromium (Cr (VI)) in the leachate of the 3D EKR system with sulfidated nano-scale zerovalent iron (S-nZVI) was more than 40% lower than those of the other 3D electrode groups, and the time required to reach the level III standard of groundwater quality criterion in China (0.05 mg/L, GB/T 14848-2017) was significantly shortened. The stabilization of Cr(VI) in contaminated soil after 3D EKR was maintained for 300 pore volumes (PVs), indicating that the treated Cr(VI) had good long-term stability. The leaching toxicity and bioaccessibility of Cr were assessed by the synthetic precipitation leaching procedure (SPLP), the toxicity characteristic leaching procedure (TCLP), and the physiologically based extraction test (PBET). The concentration of Cr(VI) in the SPLP, TCLP, and PBET leachates of the S-nZVI group decreased by more than 25% compared to the other 3D electrode groups, corresponding to the decrease in leaching toxicity and bioavailability of the treated Cr during the 15-day remediation period. In addition, the germination rate of wheat seeds and the average biomass of wheat seedlings in the S-nZVI group under alkaline conditions (EE) were higher than those in the non-polluting group (Blank-OH), indicating that the remediated soil had no obvious toxicity to wheat. In summary, 3D EKR achieved a satisfactory and stable remediation effect on Cr-contaminated soil, especially when using S-nZVI as the 3D electrode.

The removal of antibiotic resistant bacteria and antibiotic resistance genes by sulfidated nanoscale zero-valent iron activating periodate: Efficacy and mechanism

Antibiotic resistant bacteria (ARB) and antibiotic resistance genes (ARGs) have drawn much more attention due to their high risk on human health and ecosystem. In this study, the performance of sulfidated nanoscale zero-valent iron (S-nZVI)/periodate (PI) system toward ARB inactivation and ARGs removal was systematically investigated. The S-nZVI/PI system could realize the complete inactivation of 1 × 108 CFU/mL kanamycin, ampicillin, and tetracycline-resistant E. coli HB101 within 40 min, meanwhile, possessed the ability to remove the intracellular ARGs (iARGs) (including aphA, tetA, and tnpA) carried by E. coli HB101. Specifically, the removal of aphA, tetA, and tnpA by S-nZVI/PI system after 40 min reaction was 0.31, 0.47, and 0.39 log10copies/mL, respectively. The reactive species attributed to the E. coli HB101 inactivation were HO• and O2•−, which could cause the destruction of E. coli HB101 morphology and enzyme system (such as superoxide dismutase and catalase), the loss of intracellular substances, and the damage of iARGs. Moreover, the influence of the dosage of PI and S-nZVI, the initial concentration of E. coli HB101, as well as the co-existing substance (such as HCO3−, NO3−, and humic acid (HA)) on the inactivation of E. coli HB101 and its corresponding iARGs removal was also conducted. It was found that the high dosage of PI and S-nZVI and the low concentration of E. coli HB101 could enhance the disinfection performance of S-nZVI/PI system. The presence of HCO3−, NO3−, and HA in S-nZVI/PI system showed inhibiting role on the inactivation of E. coli HB101 and its corresponding iARGs removal. Overall, this study demonstrates the superiority of S-nZVI/PI system toward ARB inactivation and ARGs removal.

Immobilization of zinc and cadmium by biochar-based sulfidated nanoscale zero-valent iron in a co-contaminated soil: Performance, mechanism, and microbial response

Mining and smelting of mineral resources causes excessive accumulation of potentially toxic metals (PTMs) in surrounding soils. Here, biochar-based sulfidated nanoscale zero-valent iron (SNZVI/BC) was designed via a one-step liquid phase reduction method to immobilize cadmium (Cd) and zinc (Zn) in a copolluted arable soil. A 60 d soil incubation experiment revealed that Cd and Zn immobilization efficiency by 6 % SNZVI/BC (25.2–26.2 %) was higher than those by individual SNZVI (13.9–18.0 %) or biochar (14.0–19.3 %) based on the changes in diethylene triamine pentaacetic acid (DTPA)-extractable PTM concentrations in soils, exhibiting a synergistic effect. Cd2+ or Zn2+ replaced isomorphously Fe2+ in amorphous ferrous sulfide, as revealed by XRD, XPS, and high-resolution TEM-EDS, forming metal sulfide precipitates and thus immobilizing PTMs. PTM immobilization was further enhanced by adsorption by biochar and oxidation products (Fe2O3 and Fe3O4) of SNZVI via precipitation and surface complexation. SNZVI/BC also increased the concentration of dissolved organic carbon and soil pH, thus stimulating the abundances of beneficial bacteria, i.e., Bacilli, Clostridia, and Desulfuromonadia. These functional bacteria further facilitated microbial Fe(III) reduction, production of ammonium and available potassium, and immobilization of PTMs in soils. The predicted function of the soil microbial community was improved after supplementation with SNZVI/BC. Overall, SNZVI/BC could be a promising functional material that not only immobilized PTMs but also enhanced available nutrients in cocontaminated soils.

Fabrication of Chitin microspheres supported sulfidated nano zerovalent iron and their performance in Cr (VI) removal

Sulfidated nanoscale zerovalent iron (S-nZVI) has been extensively studied for the reductive removal of Cr(VI), but its applicability is limited by agglomeration and unexpected efficiency reduction. In this study, chitin microsphere supported sulfidated nanoscale zero-valent iron (S-nZVI@Chi-M) was prepared by in-situ one-step reduction method and used to remove Cr(VI) from water. Compared to chitin and chitosan powder, Chi-M with nanofibrous structure and large surface area performed best in stabilizing S-nZVI with a Fe0 loading content of 3.01 wt%. The S-nZVI particles were homogeneously distributed on the surface of Chi-M, effectively avoiding agglomeration. Compared with bare nanoparticles and supported nZVI, S-nZVI@Chi-M showed significantly enhanced Cr(VI) removal capacity (924.5 mg Cr(VI) for per gram of effective Fe0). The influences of sulfidation degree, dosages, initial Cr(VI) concentration, pH, DO, humic acid and typical ions on Cr(VI) removal kinetics were further studied. S-nZVI@Chi-M could be recycled for at least 4 times with acceptable reactivity. The mechanism investigation results indicated that the Cr(VI) removal was a complex process of reduction, adsorption and co-precipitation under the synergistic effect of Chi-M and S-nZVI. This work provides new ideas for the continuous fabrication of highly reactive nanoparticles, hopefully expanding the application scope of biomass resources in pollution remediation.

New insights into the degradation of nitrobenzene by activated persulfate with sulfidated nanoscale zero-valent iron: Synergistic effects of reduction and reactive oxygen species oxidation

In recent years, nitrobenzene (NB) leakage has emerged as one of the most pressing environmental issues related to groundwater contamination that requires immediate attention. This study aimed to combine S-nZVI reduction with persulfate (PDS) oxidation for NB degradation in aquatic environment. The strong synergistic effect of reduction and oxidative degradation of NB in the S-nZVI/PDS system was demonstrated for the first time. To throughly investigate the mechanism of PDS activation by S-nZVI, chemical quenching tests, detection of electron spin resonance (ESR), and monitoring of oxidant consumption were conducted. According to the results, the reactive oxygen species in the reaction system originated predominantly from the presence of ≡Fe2+ on the surface of S-nZVI and from the free state of Fe2+ in the co-activation of PDS in solution. The main role of S(-II) on the surface of S-nZVI is to enhance the electron transfer ability and act as an electron donor to facilitate the conversion between Fe2+ and Fe3+. In addition, density functional theory calculations was used to reveal the reactive sites of NB and clarify the possible degradation pathways of NB. The results of this study will deepen the understanding of the mechanism of S-nZVI driven persulfate activation and provide fundimental support for the future practical application of the S-nZVI/PDS system for the remediation of nitrobenzene contaminated groundwater.

Comparison of trichloroethylene dechlorination in seawater by sulfidated nanoscale zero-valent iron particles prepared by two methods

Sulfidated nanoscale zero-valent iron (S-nZVI) particles have demonstrated great potential in the remediation of trichloroethylene (TCE) due to their high reactivity and electron selectivity. However, very few studies have been carried out to investigate their application in salinity water or seawater. In this work, two kinds of S-nZVI particles were prepared through different methods including the chemical reduction method (CH-S-nZVI) and the bioprecipitation method (BP-S-nZVI), and then their performances in TCE remediation in seawater environment were thoroughly compared. The results suggested that the TCE removal by CH-S-nZVI particles in seawater is reduced compared to that in fresh water. However, the difference is negligible for BP-S-nZVI particles. It indicates that the seawater has a relatively strong inhibitory effect on the TCE degradation by CH-S-nZVI, but the inhibition for BP-S-nZVI is very weak. Furthermore, this work verified that sodium chloride and organic matters have obvious inhibitory effects on the TCE dichlorination, while coexisting ions such as NO3-, SO42- and Mg2+ are helpful to the degradation of TCE. The research proved that the performance of BP-S-nZVI particles in seawater is superior to CH-S-nZVI particles, providing a suitable candidate for the treatment of polluted aquifers in coastal and near-shore areas.

Synthesis of carboxymethyl cellulose stabilized sulfidated nanoscale zero-valent iron (CMC-S-nZVI) for enhanced reduction of nitrobenzene

Sulfidated nanoscale zero-valent iron (S-nZVI) had been widely applied for in situ groundwater remediation, but it still suffered from aggregation, surface passivation, and low reactivity in the reaction system. Herein, sodium carboxymethyl cellulose (CMC) was used as a stabilizer, and the effects of the CMC on the physicochemical properties, reactivity, and reusability of S-nZVI on nitrobenzene (NB) degradation were investigated. The characterizations revealed that the CMC improved the degree of sulfidation and accumulated more FexSy phase on the particle surface. The NB degradation rate by Fe/CMC mass ratio of 0.25 was the highest, and its pseudo-first order degradation rate constant (0.203 min−1) was nearly 15 times higher than that of S-nZVI (0.014 min−1), mainly because CMC significantly inhibited the surface oxidation of S-nZVI, improved the hydrophobicity, and reduced the electron transfer resistance compared to S-nZVI. Meanwhile, CMC-S-nZVI exhibited superior reusability than S-nZVI on NB degradation. The product distribution indicated that almost all NB was reduced to aniline (AN) without accumulation of intermediate after reaction. Besides, the effects of initial NB concentration, initial pH, S/Fe molar ratio, and particles dosage on NB degradation by CMC-S-nZVI were also investigated systematically. These results suggested that CMC-S-nZVI provided better reactivity and reusability than S-nZVI, which can guide the optimal design of robust CMC-S-nZVI and display great potential for in situ remediation application.

Simultaneous Activation of Peroxydisulfate and Hydrogen Peroxide by Sulfidated Nanoscale Zero-Valent Iron for Efficient MTBE Degradation: Significant Role of Oxygen Vacancy

Simultaneous Activation of Peroxydisulfate and Hydrogen Peroxide by Sulfidated Nanoscale Zero-Valent Iron for Efficient MTBE Degradation: Significant Role of Oxygen Vacancy

Enhanced oxidative and adsorptive removal of arsenite by the heterogeneous interfacial reaction of sulfidated nanoscale zerovalent iron

After sulfidation, sulfur is doped into the iron core, endowing S-nZVI with lower corrosion, stronger adsorption and interfacial oxidation of As(iii). Arsenic atoms diffuse the inner area and form arsenic sulfide stabilizing in the S-nZVI core.

Enhanced reductive degradation of tetrabromobisphenol A by biochar supported sulfidated nanoscale zero-valent iron: Selectivity and core reactivity

A core-shell structure of sulfidated nanoscale zero-valent iron deposited on biochar (S-nZVI/BC) was synthesized and the performance of S-nZVI/BC on tetrabromobisphenol A (TBBPA) degradation was investigated. Detailed characterizations indicated that controlling S content altered distribution of S species (i.e., S2-, S22-, and Sn2-) in shell and core and achieved higher hydrophobicity and lower electron-transfer resistance. S-nZVI/BC was highly reactive (∼4.3–11.3 times) and selective (∼78.9–152.6 times) over nZVI/BC for TBBPA degradation. Besides, BC improved reactivity and selectivity of S-nZVI by 0.17 and 1.35 times, respectively, deriving from increased electron-transfer, enhanced hydrophobicity, and more surface reduced S species. Thus, sulfidation and BC enhanced reactivity and selectivity of S-nZVI/BC by combining respective merits. Effects of initial TBBPA concentration, pH, and particles dosage on TBBPA degradation by S-nZVI/BC were also investigated. Remarkably, mechanism investigation revealed that core properties instead of shell dominated reactivity and TBBPA debromination mainly involved direct electron-transfer rather than atomic H.

Insights into enhanced removal of fluoranthene by sulfidated nanoscale zero-valent iron: In aqueous solution and soil slurry

In this study, 90.9% fluoranthene (FLT) was degraded in sodium percarbonate (2Na2CO3·3H2O2, SPC) oxidation system by Fe(II) combined with sulfidated nano zero valent iron (S-nZVI) activation within 60 min in aqueous solution. Scavenging experiments and electron paramagnetic resonance detection suggested that HO•, O2−•, and 1O2 contributed to the removal of FLT in SPC/Fe(II)/S-nZVI system. Based on the FLT degradation intermediates that were analyzed by GC-MS in SPC/Fe(II)/S-nZVI process, three potential FLT degradation pathways were speculated. The removal efficiency of FLT was inhibited with the presence of humic acid (HA) unless the concentration of HA was controlled at 1.0 mg L−1, and the presence of 1.0 mg L−1 HA favored the generation of HO•. The excellent removal performance of FLT (88.6%) could be achieved in actual groundwater by increasing the chemical dosages and adjusting the initial solution pH to acid environment. In soil slurry tests, the optimal reaction time and soil/water ratio were obtained as 24 h and 2/10, respectively, and the desired FLT degradation performances were obtained at pH 3 and 5 with the soil/water ratio of 2/10. This work effectively demonstrates the application potential of SPC/Fe(II)/S-nZVI system for the remediation of PAHs contamination in actual industrial sites.