Sulfidated Nano Zerovalent Iron Research Articles

Activation of persulfate by a layered double oxide supported sulfidated nano zero-valent iron for efficient degradation of 2,2′,4,4′-tetrabromodiphenyl ether in soil

The nano zero-valent iron (nZVI) activated persulfate (PS) is recognized as a promising approach to degrade 2,2′,4,4′-tetrabromodiphenyl ether (BDE-47), which is ubiquitous in the soil at electronic waste sites. However, all the reported studies were performed in liquids, gaps in the real behaviour and microbial contribution to the degradation of BDE-47 in soil media need to be urgently filled. The removal efficiency of BDE-47 is low using traditional nZVI as activator because of its aggregation and corrosion. Herein, we designed a novel layered double oxide supported sulfidated nano zero-valent iron (S-nZVI@LDO) composite and explored the performance of S-nZVI@LDO/PS to remediate BDE-47 contaminated soil. The results showed that S-nZVI@LDO has excellent stability and superior reduction capability. It could couple PS to achieve a rapid and efficient degradation of BDE-47, and the removal efficiency reached 92.31 % (5 mg/kg) within 6 h, which was much higher than that of n-ZVI/PS (53.38 %) or S-nZVI/PS (75.69 %). The kinetic constant of BDE-47 degradation by S-nZVI@LDO/PS was 23.6 and 3.7 times higher than that by single S-nZVI@LDO and nZVI/PS, respectively. It is attributable to the efficient production of SO4•-, •OH, O2•-, and 1O2 in the system, in which SO4•- and •OH dominated. The bioinformatic analysis demonstrate that soil remediation by S-nZVI@LDO/PS significantly enriched aromatic compounds-degrading bacteria and increased the abundance of hydrocarbon degradation functions. Microbial degradation may play important roles in the BDE-47 degradation and soil quality recovery. The identification of degradation pathways suggests that BDE-47 was degraded to very low-toxic products based on GHS toxicity prediction through a series process of debromination, hydroxylation, cleavage central oxygen, and ring opening, or even completely mineralized. The findings may provide significant implications for the in-situ clean-up of brominated flame retardants in contaminated soil using S-nZVI@LDO/PS Fenton-like system.

Quantifying remediation of chlorinated volatile compounds by sulfidated nano zerovalent iron treatment using numerical modeling and CSIA

Sulfidated nanoscale zerovalent iron (S-nZVI) has demonstrated promising reactivity and longevity for remediating chlorinated volatile compounds (cVOC) contaminants in laboratory tests. However, its effectiveness in field applications remains inadequately evaluated. This study provides the first quantitative evaluation of the long-term effectiveness of carboxymethyl cellulose-stabilized S-nZVI (CMC-S-nZVI) at a cVOC-contaminated field site. A reactive transport model-based numerical approach delineates the change in cVOC concentrations and carbon isotope values (i.e., δ13C from compound-specific stable isotope analysis (CSIA)) caused by dissolution of dense non-aqueous phase liquid, sorption, and pathway-specific degradation and production, respectively. This delineation reveals quantitative insights into remediation effectiveness typically difficult to obtain, including extent of degradation, contributions of different degradation pathways, and degradation rate coefficients. Significantly, even a year after CMC-S-nZVI application, degradation remains an important process effectively removing various cVOC contaminants (i.e., chlorinated ethenes, 1,2-dichloroethanes, and chlorinated methanes) at an extent varying from 5 %-62 %. Although the impacts of CMC-S-nZVI abundance on degradation vary for different cVOC and for different sampling locations at the site, for the primary site contaminants of tetrachloroethene and trichloroethene, their predominance of dichloroelimination pathway (≥ 88 %), high degradation rate coefficient (0.4–1.7 d-1), and occurrence at locations with relatively high CMC-S-nZVI abundance strongly indicate the effectiveness of abiotic remediation. These quantitative assessments support that CMC-S-nZVI supports sustainable ZVI-based remediation. Further, the novel numerical approach presented in this study provides a powerful tool for quantitative cVOC remediation assessments at complex field sites where multiple processes co-occur to control both concentration and CSIA data.

Effect of physical and chemical co-application of biochar and sulfidated nano scale zero valent iron on the NB degradation in soil: Key roles of biochar

Sulfidated nano zero-valent iron (S-nZVI) can efficiently degrade nitrobenzene (NB) in water. However, its practical application in soil remediation is constrained by limited contact with soil-sorbed NB, leading to sparse research. Herein, Biochar (BC), with its notable adsorption capacity, was coupled with S-nZVI to assess the role of physical (S-nZVI + BC) and chemical (S-nZVI@BC) co-application of BC and S-nZVI, respectively, on enhancing NB degradation in soil. Regardless of the physical or chemical co-application, there was a remarkable advantage after addition of BC relative to S-nZVI alone. In physical co-application, the NB degradation rate of S-nZVI + BC increased as the increasing BC concentration from 0 to 3.5 g·L−1, attributed to enhanced NB desorption via the solubilization effect of BC, facilitating interaction with S-nZVI. Beyond this concentration, no significant improvement was observed, possibly due to BC obstructing reactive sites on S-nZVI surface. In chemical co-application, the S-nZVI@BC (S-nZVI/BC mass ratio of 1:1) exhibited a high NB degradation rate constant (1.097 h−1) during reaction. Apart from solubilization effect, BC in S-nZVI@BC endowed S-nZVI with a higher anti-oxidation property, hydrophobicity, electron transfer capacity, and dispersion effect, accounting for the higher reactivity of S-nZVI@BC over S-nZVI + BC. Besides, the water/soil ratio and initial soil pH significantly affected NB degradation rate, with the optimum water/soil ratio and initial soil pH being 3 and 5, respectively. Our finding broadens the applicability of BC and may offer a highly effective way in soil remediation.

Efficient U(VI) removal by Ti3C2Tx nanosheets modified with sulfidated nano zero-valent iron: Batch experiments, mechanism, and biotoxicity assessment

The MXenes, a new class of two-dimensional layered materials, have found extensive applications in water treatment for its excellent thermal stability, electrical conductivity, and excellent adsorption ability. Sulfidized nano zero-valent iron (S-nZVI) is a good reducing agent, however, the practical application of S-nZVI is currently restricted due to the tendency of nano materials to agglomerate. Herein, MXenes use as a support and in situ loading S-nZVI on it to prepare a new material (S-nZVI/Ti3C2Tx), and applied it to U(VI) removal in water treatment. The microscopic characterization proves that S-nZVI on Ti3C2Tx has good dispersion and effectively alleviates agglomeration. Batch experiments shown that S-nZVI/Ti3C2Tx has a very good effect on U(VI) removal, and the maximum adsorption capacity reaches 674.4 mg/g under the aerobic condition at pH=6.0. The pseudo-second-order kinetic model and the Langmuir isotherm model were found to be more appropriate for describing the adsorption behavior. This indicates that the removal process is a single molecular layer chemisorption. Moreover, the S-nZVI/Ti3C2Tx maintained a removal efficiency of over 85 % for U(VI) even after being reused five times, demonstrating its excellent reusability. It is worth noting that the material can remove 79.8% of 50 mg/L of U(VI) in simulated seawater, indicating that S-nZVI/Ti3C2Tx possessed an excellent uranium extraction performance from seawater. Experimental results and XPS analysis showed that U(VI) was removed by adsorption, reduction and co-precipitation. Moreover, S-nZVI/Ti3C2Tx was a low toxicity material to hyriopsis cumingii. Therefore, S-nZVI/Ti3C2Tx was expected to be a candidate as adsorbent with great potential in removal of uranium from wastewater and seawater.

Synergistically enhancing the remediation of low C/N slightly black-odorous water body using pretreated stalk in-situ loaded with sulfidated nano zero-valent iron

Sulfidated nano zero-valent iron (S-NZVI) as reductants coupled with organic carbon are promising in enhancing denitrification which is crucial for remediation of low C/N water body. Nevertheless, the dearth of research on the effectiveness of these materials in actual water remediation limits their application. Additionally, most of the studies utilizes industrial chemical-derived organic carbon, which exacerbates environmental and economic burdens. This study proposes employing pretreated stalks in-situ loaded S/Fe (SS-S/Fe) to remediate the low C/N slightly black-odorous water body. The pretreated stalk acts as carbon source replacing the industrial chemicals. The pretreatment process was carried out by using H2O2 and acetic acid to decrease the lignin content. The 2, 4-dichlorophenol was utilized as a target pollutant for optimization of materials. The sediment from the water body was remediated, the impact of SS-S/Fe on water body and microbial community structure were clarified. The lignin residues in the stalk were found to enhance the dispersity, O2 resistance, and reduction performance toward 2, 4-dichlorophenol of S/Fe. S/Fe facilitates 2, 4-dichlorophenol degradation via reduction and TP removal via forming Fe-P precipitation. SS plays a significant role in TN removal, assisting in enhancing the 2, 4-dichlorophenol and TP removal performance of S/Fe. Crucially, SS and S/Fe synergistically boost sediment microbial activity, conferring resistance to the subsequent pollution shock. The decisive role of SS in enhancing denitrification by cultivating Anaeromyxobacter, unclassified_f_Comamonadaceae, norank_f_norank_o_norank_c_Anaerolineae and Thiobacillus has been demonstrated. This study improves S-NZVI applicability in actual low C/N water bodies and provides new methods for utilizing stalk resources.

Application of sulfidated nano zero-valent iron to enhance fluoranthene degradation by Fe(III) activated sodium percarbonate process in aqueous and soil media

Iron sludge generation poses a challenge to the application of Fenton/Fenton-like processes in wastewater treatment. In this study, sulfidated nano zero-valent iron (S-nZVI) was introduced to enhance the activation of sodium percarbonate (SPC) by Fe(III), mitigating the generation of iron sludge by promoting the Fe(III)/Fe(II) cycle. The proposed technique efficiently removed 94.3 % fluoranthene (FLT) in which HO• acted as the major reactive oxygen species responsible for FLT degradation. Toxicity analysis revealed phthalic acid and 1-phenylnaphthalene as FLT degradation intermediates which finally converted to CO2 and H2O. Similarly, the luminous bacteria experiment also showed that the FLT degradation process was environmentally benign. The support of S-nZVI to the Fe(III)/Fe(II) cycle was determined by analyzing the morphology and characterization of S-nZVI. The removal of FLT reached more than 80 % at pH ranging from 3.0 to 10.0, and the detrimental effects of low concentrations of Cl− were mitigated. SPC/S-nZVI/Fe(III) process showed good removal of FLT (90 %) in both real groundwater and river simulation experiments. Furthermore, SPC/S-nZVI/Fe(III) process was successfully applied in soil slurry media with around 90 % FLT degradation in 12 h. The influence of the soil/water ratio on FLT removal was found to be negligible. SPC/S-nZVI/Fe(III) process was superior for the removal of mixed FLT, naphthalene, and phenanthrene contamination. In conclusion, the SPC/S-nZVI/Fe(III) system exhibits enormous potential in the remediation of polycyclic aromatic hydrocarbons (PAHs) contaminated sites.

Sulfidated nano zero-valent iron activated peracetic acid for ciprofloxacin degradation: Performance and mechanism

As commonly observed water pollutants, antibiotics can induce antibiotic-resistance genes and pose significant risks to ecosystems and human health. Consequently, eliminating antibiotics from water environments is essential. We used the sulfidated nano zero-valent iron (S-nZVI) to activate peracetic acid (PAA) system to facilitate ciprofloxacin (CIP) degradation. S-nZVI was fabricated using the liquid-phase method, yielding particles with a predominantly spherical morphology and an average size range of 70–110 nm. Under optimized conditions, the S-nZVI/PAA system had a remarkable CIP removal efficiency of 95.61 % in 60 min. The reactive oxygen species (ROS) and Fe species (Fe(IV)) generated in the S-nZVI/PAA system were fundamental in facilitating the degradation of CIP. The reaction products of CIP were identified, and the toxicity was reduced after degradation. Additionally, an investigation was conducted to explore the practical application potential of the S-nZVI/PAA system. The work provides a promising strategy for the removal of antibiotics in water, and gives new insights into the mechanism of S-nZVI activating PAA to remove antibiotics.

Novel Oxidation Strategies for the In Situ Remediation of Chlorinated Solvents from Groundwater—A Bench-Scale Study

Industrial chlorinated solvents continue to be among the most significant issues in groundwater (GW) pollution worldwide. This study assesses the effectiveness of eight novel oxidation treatments, including persulfate (PS), ferrous sulfate, sulfidated nano-zero valent iron (S-nZVI), and potassium ferrate, along with their combinations, for the potential in situ remediation of GW polluted with chlorinated solvents (1,2-dichloroethylene, trichloroethylene, and tetrachloroethylene). Our bench-scale results reveal that the combined addition of PS and S-nZVI can effectively eliminate trichloroethylene (10 µg/L), achieving removal rates of up to 80% and 92% within 1 h, respectively, when using synthetic GW. In the case of real GW, this combination achieved removal rates of 69, 99, and 92% for cis-1,2-dichloroethylene, trichloroethylene, and tetrachloroethylene, respectively, within 24 h. Therefore, this proposed remediation solution resulted in a significant reduction in the environmental risk quotient, shifting it from a high-risk (1.1) to a low-risk (0.2) scenario. Furthermore, the absence of transformation products, such as vinyl chloride, suggests the suitability of employing this solution for the in situ remediation of GW polluted with chlorinated solvents.

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.

Attapulgite-supported sulfidated nano Zero-Valent Iron activated persulfate advanced oxidation technology for degradation of polyethylene microplastics: Optimal design, change of particle size and degradation mechanisms

Microplastics (MPs), as a novel pollutant, have raised concerns about their potentialtoxicity and the wide-ranging ecological risks they may pose. In this study, a novel attapulgate-supported sulfidized nanoscale zero-valent iron (S-nZVI@ATP) catalyst was prepared for the activation of persulfate. We investigated the degradation efficiency and mechanism of polyethylene microplastics (PE) using the S-nZVI@ATP activated persulfate advanced oxidation process. Various factors, such as temperature,pH, catalyst dosage, and persulfate concentration, were evaluated for their influence on the oxidative reaction in the system to determine the optimal degradation conditions. The average particle size of PE decreased from 64.2±0.86μm to 28.1±0.91μm after 24 hours of oxidative degradation. The reaction progressed, TOC in the solution showed an initial increase, followed by a decrease. Some PE was oxidized into small molecules substances such as alkanes, alkenes, ketones, alcohols, and carboxylic acids. S-nZVI@ATP continuously supplied Fe2+ for persulfate activation, generating strong oxidants SO4•-, •OH, and 1O2, among which SO4•- played a dominant role in oxidation system. The heterogeneous advanced oxidation system provided in this study offers an effective reference for PE degradation and holds great promise as a method for degrading MPs in water.

Fluoranthene degradation in a persulfate system activated by sulfidated nano zero-valent iron (S-nZVI): performance and mechanisms.

Fluoranthene (FLT) has received mounting focus due to its hazardous properties and frequent occurrence in groundwater. In this study, sulfidated nano zero-valent iron (S-nZVI) was selected as an efficient catalyst for activating persulfate (PS) to degrade FLT. The effects of reagent doses, various water conditions (pH, anions, and humic acid), and the presence of surfactants on FLT degradation were investigated. Radical probe experiments, electron paramagnetic resonance (EPR) spectrum detection, and scavenging tests were performed to identify the major reactive oxygen species (ROS) in the system. The results showed that in the PS/S-nZVI system, 96.2% of FLT was removed within 120 min at the optimal dose of PS = 0.07 mM and S-nZVI = 0.0072 g L-1. S(-II) in the S-nZVI surface layer promoted Fe(II) regeneration. Furthermore, HO• and SO4-• were identified as the main contributors to FLT degradation. The intermediates of FLT degradation were detected by gas chromatograph-mass spectrometry (GC-MS) and a possible FLT degradation pathway was proposed. Finally, the effective degradation of two other common polycyclic aromatic hydrocarbons (PAHs) (naphthalene and phenanthrene) demonstrated the broad-spectrum reactivity of the PS/S-nZVI process. In conclusion, these findings strongly demonstrate that the PS/S-nZVI process is a promising alternative for the remediation of PAH-contaminated groundwater.

Performance evaluation of sulfidated nanoscale iron for hexavalent chromium removal from groundwater in sequential batch study.

Chromium [Cr] contamination in groundwater is one of the serious environmental concerns due to the carcinogenicity of its water-soluble and mobile hexavalent [Cr(VI)] form. In spite of the existence of multiple precipitation and adsorption-based Cr(VI) remediation technologies, the usage of sulfidated nano zerovalent iron (S-nZVI) has recently attracted researchers due to its high selectivity. Although S-nZVI effectively immobilized Cr(VI), its long-term performance in multiple shifted equilibrium has not been explored. In this contribution, influences of S-nZVI dosage, initial concentration of Cr(VI), pH, ionic strength, total hardness, sulfate, carbonate, and silicate were probed in ultrapure water. Further experiments were performed in synthetic groundwater to investigate the effects of initial concentration of Cr(VI) in the pH range of 4-8 for 1g L-1 S-nZVI dosage. Cr(VI) removal rate was quantified in groundwater without pH fixation. Finally, a comparative study between conventional nano zerovalent iron (nZVI) and S-nZVI was conducted in sequential batch reactors to investigate their respective efficiencies during repeated usage. Mechanistic interpretation of the processes governing the immobilization of Cr(VI) was done by integrating the results of these experiments with the metadata. While aggregation due to magnetic properties and rapid oxidation of Fe decreased the efficiency of nZVI with repeated usage, sulfidation minimized the passivation and favored an extended reducing environment because of continuous electron transfer from iron and sulfur components.

Relationship Between Sulfidated Nano Zero Valent Iron and a Reductive Dechlorinating Microbial Culture - Synergistic or Antagonistic?

Sulfidated nano zerovalent iron (S-nZVI) has garnered significant attention from researchers due to its potential for effective in-situ remediation applications. Compared to bare nZVI, sulfidation process enhances its reactivity towards chlorinated volatile organic compounds (cVOCs) and improves its longevity (Nunez Garcia et al. 2021). Stabilizing the particles with a polymer, like carboxymethyl cellulose (CMC), can further improve the performance of S-nZVI by imparting higher stability, less toxicity towards microbial cells, and a potential biostimulatory effect, making CMC-S-nZVI a promising in-situ remediation technology (Nunez Garcia et al. 2021). Recently, CMC-S-nZVI has also been applied for field-scale remediation (Nunez Garcia et al. 2020;Brumovský et al. 2021). The contaminated sites usually have multiple pollutants and not all can be degraded by CMC-S-nZVI, thus, leaving some recalcitrant cVOCs untreated (Zhang et al. 2021). Biodegradation of cVOCs by dechlorinating microbial cultures may generate highly toxic intermediates like vinyl chloride (Kocur et al. 2016). However, coupling the two treatments may be able to compensate for each other’s drawbacks, resulting in higher efficiency, longer effectiveness, non-accumulation of intermediates, and degradation of a wider range of target contaminants. However, interacting effects of CMC-S-nZVI on dechlorinating microbial cultures have not been studied yet. This research investigates the potential of combining CMC-S-nZVI and a reductive dechlorinating microbial culture (KB-1) to degrade trichloroethylene (TCE) and 1,2-dichloroethane (1,2-DCA). CMC-S-nZVI was synthesized by a two-step method: (1) CMC-nZVI was first synthesized by reducing ferrous sulfate-CMC solution with dropwise addition of sodium borohydride solution with continuous mixing and (2) then sodium dithionite solution was added as a sulfidation agent to the freshly-synthesized CMC-nZVI (Nunez Garcia et al. 2020). Effects of different sulfur-iron ratios (S/Fe), iron, and CMC concentrations on TCE degradation were studied to obtain an effective CMC-S-nZVI formulation. Results showed a successful TCE removal by the CMC-S-nZVI but 1,2-DCA was not degraded. TCE degradation by CMC-S-nZVI fitted the first-order kinetic model, with the highest degradation rate constant (0.35 h-1) achieved at S/Fe = 0.1 with iron and CMC concentrations of 1 gL-1 and 0.4 wt%, respectively. This CMC-S-nZVI formulation was further tested to examine its interaction with KB-1 in terms of cVOCs dechlorination and microbial population responses. A four-day aged CMC-S-nZVI was also tested to study the effect of aging. Degradation pathways for TCE and 1,2-DCA were proposed, based on the formation of degradation products. For the coupled treatment, an increase in microbial abundance was observed by quantifying DNA concentrations. This demonstrated a synergistic relationship between CMC-S-nZVI and KB-1. Unlike the CMC-S-nZVI only treatment, microcosms containing both CMC-S-nZVI and KB-1 were found to successfully degrade the 1,2-DCA. The coupled treatment degraded TCE and 1,2-DCA at faster rates and generated lesser amounts of vinyl chloride than the KB-1 only treatment, confirming the biostimulatory effect of CMC-S-nZVI. In the KB-1 only treatment with CMC as the sole carbon and energy source, TCE and 1,2-DCA were successfully dechlorinated. Transmission electron microscopy illustrated that CMC-S-nZVI particles were attached to the microbes but did not penetrate the bacterial cells. In summary, synergistic abiotic-biotic dechlorination of TCE and 1,2-DCA was achieved by the combined treatment of CMC-S-nZVI and KB-1, suggesting that multi-contaminant sites can benefit from this approach. Additionally, the four-day aged CMC-S-nZVI performed similar to the freshly-synthesized one, demonstrating that the field-scale remediation can have a more feasible time scale for the preparation and application of these amendments.

Subsurface Transport of Sulfidated Nano Zero Valent Iron and In Situ Biogeochemical Transformation of Chlorinated Solvents: A Field Study

In situ chemical reduction of chlorinated volatile organic compounds (cVOCs) by nano zero-valent iron (nZVI) has been widely applied in the past 20 years, but with limited effectiveness for bare nZVI due to rapid particle settling, short lifespan, and low reactivity. Stabilization and sulfidation of nZVI have improved its mobility and longevity, increased reactivity towards cVOCs, and reduced toxicity to microbes (Nunez Garcia et al. 2021). In the first-ever CMC-S-nZVI field trial, nZVI sulfidated by dithionite (S-nZVI) and stabilized by carboxymethyl cellulose (CMC) was injected into the subsurface of a site contaminated with a wide range of cVOCs. Multi-level wells were installed to monitor the transport of the CMC-S-nZVI suspension and its remedial performance for two years. Short-term (0-17 days) monitoring demonstrated a good transport of the suspension in the down- and up-gradient wells, in terms of total iron, boron, and sulfides which were major constituents of CMC-S-nZVI. Changes in concentrations of parent compounds, intermediates, and ethene showed effective dechlorination of high-chlorinated VOCs such as tetrachloroethene (PCE) and carbon tetrachloride (Nunez Garcia et al. 2020a, Nunez Garcia et al. 2020b). Long-term (157-729 days) performance was evaluated through temporal analyses of microbial communities, total iron, boron, and cVOCs in groundwater samples. Microbial populations, including organohalide-respiring bacteria, increased by >1 order of magnitude; with Geobacter being the most abundant. This long-term enrichment can be attributed to the low toxicity of CMC-S-nZVI and biostimulation by CMC and perhaps Fe3+. Non-metric multidimensional scaling analysis was carried out on microbial data grouped by depth range and proximity to the injection well. At locations that clearly received CMC-S-nZVI, there was a significant shift in microbial communities that was sustained for the long term. Iron concentrations increased substantially in long-term samples while boron concentrations decreased, suggesting that this iron did not come from CMC-S-nZVI. Microbial dissolution of iron minerals might have contributed to the increased iron content (Jones et al. 2006). Excess dithionite in CMC-S-nZVI would also have reductively dissolved native iron from the soil, as successfully demonstrated in the in situ redox manipulation (ISRM) technology wherein subsurface Fe3+ in soil was reduced to Fe2+ for long-term remedial purposes (Vermeul et al. 2000). Long-term changes in concentrations of lesser-chlorinated VOCs and hydrocarbons suggest that PCE was degraded via both the microbially-mediated sequential hydrogenolysis as well as the abiotic β-elimination. The intermediate vinyl chloride (VC) surprisingly did not accumulate in the current study, in contrast to the significant VC accumulation in a previous un-sulfidated CMC-nZVI trial at the same location (Kocur et al. 2016). Excess dithionite injected in this study might have avoided VC accumulation, as previously reported for ISRM treatment of a cVOCs-contaminated site (Vermeul et al. 2000). Additionally, the identified bacterial populations might have utilized sulfur species (from dithionite decomposition) and iron to form iron sulfides, which could dechlorinate cVOCs via in situ biogeochemical transformation (Kennedy et al. 2006). In summary, this study has demonstrated the long-term efficiency of CMC-S-nZVI for cVOCs removal through a combination of abiotic, biotic, and biostimulatory processes in the subsurface.

Interaction of chromium-sulfur-iron during Cr(VI) stabilization by polysulfide-modified nanoscale zero-valent iron for groundwater remediation: Batch experiments and numerical simulation

Sulfidated nano zero-valent iron (nZVI) is a vital technology for stabilizing hexavalent chromium (Cr(VI)) in groundwater. However, it faces challenges such as oxidation susceptibility and unclear reaction mechanisms. In this study, a novel CaSx-modified nZVI material (PS-nZVI) was synthesized through an improved preparation method by using a two-step method to investigate its interactions with chromium, sulfur and iron for Cr(VI) immobilization. Results showed that the addition of PS significantly altered the microstructure and properties of the material. As the PS content increased, the material transformed from nZVI to a flower-like FeSn structure, enhancing its reduction capability and protecting the internal nZVI. PS-nZVI exhibited higher Cr(VI) removal capacity compared to nZVI, with the best efficiency at a PS/Fe molar ratio of 1/10. The removal process followed a pseudo-second-order kinetic model, indicating that chemical adsorption dominated. Initially, PS-nZVI focused on reducing Cr(VI), differentiating it from other sulfide-modified nZVI. The formation of FeSn on the surface of material facilitated the reduction of Fe(III) and Cr(VI) and acted as an electron transfer intermediate, enabling efficient Cr(VI) stabilization. Using a reactive transport model, it can be found that iron contributed 57.4% to Cr(VI) solidification as chromite, while sulfur and iron contributed 95.9% and 4.1%, respectively, to Cr(VI) reduction to Cr(III).

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.

Synergistic effect of sulfidated nano zerovalent iron and proton-buffering montmorillonite in reductive immobilization of alkaline Cr(VI)-contaminated soil

Effective remediation of Cr(VI)-contaminated soil with strong alkalinity and high Cr(VI) concentration is a severe challenge. Herein, a proton-buffering montmorillonite-supported sulfidated nano zerovalent iron (nFeS/Fe0@H–Mt) was developed for remediation of alkaline Cr(VI)-contaminated soil. The reductive efficiencies of water-soluble Cr(VI) reached 99.7%, 99.3% and 99.8% in three tested soils with initial concentrations of 439.6, 3307.5 and 4626.7 mg kg−1, respectively, after 15 d of nFeS/Fe0@H–Mt treatment. Further speciation analyses demonstrated most available Cr species (exchangeable and carbonate-bound Cr) were transformed into more stable Cr species. The leachable Cr(VI) and total Cr obtained by toxicity leaching procedures decreased to extremely low levels and maintained long-term stability for 120 d. Such superior reductive immobilization performance of FeS/Fe0@H–Mt was attributed to the synergistic effect of sulfidated nano zerovalent iron and proton-buffering montmorillonite, which induced the coordination of proton donation and electron transfer. The proton-buffering montmorillonite (H–Mt) could prevent the aggregation of nanoparticles and provide protons to accelerate the corrosion of Fe0. In addition, the FeS component improved electron selectivity and facilitated electron transfer of Fe0 to Cr(VI). Our study demonstrated that the coordination of proton donation and electron transfer significantly enhanced the Cr(VI) reduction under the alkaline condition thus leading to effective remediation of alkaline Cr(VI)-contaminated soil.

Simultaneous stabilization of Pb, Cd, and As in soil by rhamnolipid coated sulfidated nano zero-valent iron: Effects and mechanisms.

Sulfidation effectively improves the electron transfer efficiency of nanoscale zero-valent iron (nZVI), but decreases the specific surface area of nZVI. In this study, sulfidated nZVI (S-nZVI) coated with rhamnolipid (RL-S-nZVI) was synthesized and used to stabilize Pb, Cd, and As in combined polluted soil. The stabilization efficiency of 0.3% (wt) RL-S-nZVI to water soluble Pb, Cd, and As in soil reached 88.76%, 72%, and 63%, respectively. Rhamnolipid coating inhibited the reduction of specific surface area and successfully encapsulated nZVI, thus reducing the oxidation of Fe0. The types of iron oxides in RL-S-nZVI were reduced compared to S-nZVI, but the content and strength of Fe0 iron were obviously enhanced. Furthermore, rhamnolipid functional groups (-COOH and -COO-) were also involved in the stabilization process. In addition, the stabilization efficiency of RL-S-nZVI to the bioavailable Pb, Cd, and As in soil increased by 41%, 41%, and 50%, respectively, compared with nZVI. The presence of organic acids, especially citric acid, improved the stabilization efficiency of RL-S-nZVI to the three metals. The result of BCR sequential extraction indicated that RL-S-nZVI increased the residual state of Pb, Cd, and As and reduced the acid-soluble and reducible state after 28 days of soil incubation. XRD and XPS analyses showed that the stabilization mechanisms of RL-S-nZVI on heavy metals involved in ion exchange, surface complexation, adsorption, co-precipitation, chemisorption, and redox.

Fabrication of Chitin Microspheres Supported Sulfidated Nano Zerovalent Iron and Their Performance in Cr(Vi) Removal

Fabrication of Chitin Microspheres Supported Sulfidated Nano Zerovalent Iron and Their Performance in Cr(Vi) Removal

Critical layer in liquid-solid system influencing the remediation of chromium using zeolite-supported sulfide nano zero-valent iron

Sulfidated nano zero-valent iron particles were immobilized on ZSM-5 zeolite (Z/S-nZVI) and used for hexavalent chromium (Cr(VI)) remediation. The performance of Z/S-nZVI improved with the increase in Cr(VI) concentration (< 60 mg/L), while the performance significantly decreased for a Cr(VI) concentration of more than 60 mg/L. The adsorption behavior for Cr(VI) was different from that reported in previous studies. The improved performance can be tailored for increasing efficiency of nano zero-valent iron (nZVI) corrosion, while the degree of corrosion of nZVI was affected by the concentration of the pollutant as discussed by kinetics, X-ray diffraction (XRD) and X-ray photoelectron spectrometer (XPS) analyses. The experiments for the dissolution of ferrous ions and the dosage of adsorbent demonstrated that the critical layer in the liquid-solid system changed with the increase in the concentration of Cr(VI) (Cr(VI): Z/S-nZVI > 0.6). Moreover, the removal mechanisms of Cr(VI) were elucidated through XRD, transmission electron microscopy (TEM) and XPS techniques. This results demonstrate that the species of chromium in the critical layer changed from Cr(III) to Cr(VI) as the concentration of chromium increased from low to high. Furthermore, the critical layer was composed of Cr(VI), Fe(II), O and H elements. Additionally, the experiments of coexisting ions and aging time confirmed that Z/S-nZVI possessed high selectivity and stability to ensure efficiency and cost-effectiveness in practical applications.