Complete 2,4,6-trichlorophenol degradation by anaerobic sludge acclimated with 4-chlorophenol: Synergetic effect of nZVI@BMPC and sodium lactate as an external nutrient.

Ball-milled plastic char supported nano zero-valent iron (nZVI@BMPC) and their application combined with anaerobic sludge for microbial dechlorination of 2,4,6-trichlorophenol (2,4,6-TCP) were investigated. The XRD and FTIR analysis proved composition of zero valent states of iron, and the BET and SEM analysis showed that nZVI was uniformly distributed on the surface of BMPC. Successive addition of 1000 mg/L sodium lactate and nZVI@BMPC enhanced the acclamation of anaerobic sludge and resulted in the degradation of 4-CP within 80 days. The acclimated consortium with nZVI@BMPC completely degraded 2,4,6-TCP into CH4 and CO2, and the key dechlorination route was through 4-CP dechlorinaion and mineralization. The degradation rate of 2,4,6-TCP with nZVI@BMPC was 0.22/d, greater than that without nZVI@BMPC. The dechlorination efficiency was enhanced in the Fe2+/Fe3+ system controlled by nZVI@BMPC and iron-reducing bacteria. Metagenomic analysis result showed that the dominant de-chlorinators were Chloroflexi sp., Desulfovibrio, and Pseudomonas, which could directly degrade 2,4,6-TCP to 4-CP, especially, Chloroflexi bacterium could concurrently be used to mineralize 4-CP. The relative abundance of the functional genes cprA, acoA, acoB, and tfdB increased significantly in the presence of the nZVI@BMPC. This study provides a new strategy can be a good alternative for possible application in groundwater remediation.

Removal of ciprofloxacin by biosulfurized nano zero-valent iron (BP-S-nZVI) activated peroxomonosulfate: Influencing factors and degradation mechanism.

Agglomeration and passivation restrict the using zero-valent iron nanoparticles (nZVI). Enhancing the reactivity of nZVI is often accomplished by sulfurization. In this work, nZVI was sulfurized using SRB to produce biosulfurized nano zero-valent iron (BP-S-nZVI), which was then utilized as a catalyst to investigating its performance in an advanced oxidation process based on activated peroxomonosulfate (PMS). When the S/Fe was 0.05, 0.4 g/L of catalyst and 0.5 mM PMS were added to a 20 mg/L ciprofloxacin solution. In 120 min, a 90.4% clearance rate was reached. When the initial pH of the solution was within the range of 3-11, all exhibited acceptable degradation performance and were minimally affected by co-existing anions. In this activation system, hydroxyl, superoxide and sulfate radicals (•OH, O2•- and SO4•-, respectively) have been proven to be the main active species. Seven intermediates in the degradation process of CIP were identified by LC-MS analysis and two possible degradation pathways were proposed. In addition, the degradation rate of CIP was still able to reach 87.0% after five cycles, and the removal rate remained unchanged in the CIP solution with actual water samples as background. This study demonstrated that BP-S-nZVI as a catalyst for the activation of PMS for CIP degradation can still show good reactivity, which provides more possibilities for the practical application of BP-S-nZVI in the degradation of pollutants.

Adsorption-coupled Fenton type reduction of bromate in water by high-yield polymer-derived ceramic-supported nano-zerovalent iron.

Nano-zerovalent iron (nZVI) is a promising material for the removal of both organic and inorganic pollutants from contaminated water. This study investigates the potential of a novel composite of nZVI on a polymer-derived supporting ceramic (nZVI-PDC) synthesized via the liquid-phase reduction method for the simultaneous adsorption and Fenton-type reduction of bromate anion (BrO3-) in water. The nZVI nanoparticles were effectively anchored onto the PDC by impregnating high-yield carbon in a ferrous sulfate solution. The PDC facilitated the uniform dispersion of nZVI nanoparticles due to its multiple active sites distributed within mesocarbon cavities. The developed nZVI-PDC composite exhibited a high specific surface area of 837 m2 g-1 and an ordered mesoporous structure with a pore volume of 0.37 cm3 g-1. As an adsorbent, the nZVI-PDC composite exhibited a maximum adsorption capacity (qe) of 842 mg g-1 and a partition coefficient (KH) of 10.2 mg g-1 µM-1, as calculated by the pseudo-second-order model. As a catalyst, the composite demonstrated a reaction kinetic rate of 43.5 µmol g-1 h-1 within 6 h at pH 4, using a dosage of 60 mg L-1 nZVI-PDC and a concentration of 0.8 mmol L-1 H2O2. Comparatively, PDC exhibited a qe of 408 mg g-1, KH of 1.67 mg g-1 µM-1, and a reaction rate of 20.8 µmol g-1 h-1, while nZVI showed a qe of 456 mg g-1, KH of 2.30 mg g-1 µM-1, and a reaction rate of 27.2 µmol g-1 h-1. The modelling indicated that the nZVI-PDC composite followed pseudo-second-order kinetics. The remarkable removal efficiency of the nZVI-PDC composite was attributed to the synergistic effects between PDC and nZVI, where PDC facilitated charge transfer, promoting Fe2+ generation and the Fe3+/Fe2+ cycle. Overall, this work introduces a promising adsorption technology for the efficient removal of BrO3- from contaminated aqueous solutions, highlighting the significant potential of the nZVI-PDC composite in water purification applications.

How does the biochar-supported sulfidized nanoscale zero-valent iron affect the soil environment and microorganisms while remediating cadmium contaminated paddy soil?

In previous studies, iron-based nanomaterials, especially biochar (BC)-supported sulfidized nanoscale zero-valent iron (S-nZVI/BC), have been widely used for the remediation of soil contaminants. However, its potential risks to the soil ecological environment are still unknown. This study aims to explore the effects of 3% added S-nZVI/BC on soil environment and microorganisms during the remediation of Cd contaminated yellow-brown soil of paddy field. The results showed that after 49 d of incubation, S-nZVI/BC significantly reduced physiologically based extraction test (PBET) extractable Cd concentration (P < 0.05), and increased the immobilization efficiency of Cd by 16.51% and 17.43% compared with S-nZVI and nZVI/BC alone, respectively. Meanwhile, the application of S-nZVI/BC significantly increased soil urease and sucrase activities by 0.153 and 0.446 times, respectively (P < 0.05), improving the soil environmental quality and promoting the soil nitrogen cycle and carbon cycle. The results from the analysis of the 16S rRNA genes indicated that S-nZVI/BC treatment had a minimal effect on the bacterial community and did not appreciably alter the species of the original dominant bacterial phylum. Importantly, compared to other iron-based nanomaterials, incorporating S-nZVI/BC significantly increased the soil organic carbon (OC) content and decreased the excessive release of iron (P < 0.05). This study also found a significant negative correlation between OC content and Fe(II) content (P < 0.05). It might originate from the reducing effect of Fe-reducing bacteria, which consumed OC to promote the reduction of Fe(III). Accompanying this process, the redistribution of Cd and Fe mineral phases in the soil as well as the generation of secondary Fe(II) minerals facilitated Cd immobilization. Overall, S-nZVI/BC could effectively reduce the bioavailability of Cd, increase soil nutrients and enzyme activities, with less toxic impacts on the soil microorganisms.

Study on the enhancement of citric acid chemical leaching of contaminated soil by modified nano zero-valent iron.

This study aimed to evaluate the effect of modified nanoscale zero-valent iron (SAS-nZVI) on chemical leaching of lead and cadmium composite contaminated soil by citric acid (CA). The synthesized SAS-nZVI was used as a leaching aid to improve the removal rate of soil heavy metals (HMs) by CA chemical leaching. The effects of various factors such as SAS-nZVI dosage, elution temperature and elution time were studied. At the same time, the effect of chemical leaching on the basic physical and chemical properties of soil and the morphology of HMs was evaluated. The results show that when the SAS-nZVI dosage is 2.0 g/L, the leaching temperature is 25 °C, and the leaching time is 720 min, the maximum removal rates of Pb and Cd in the soil are 77.64% and 97.15% respectively. The experimental results were evaluated using elution and desorption kinetic models (Elovich model, double constant model, diffusion model). The elution and desorption process of Pb and Cd in soil by SAS-nZVI-CA fitted well with the double-constant model, indicating that the desorption kinetic process of Pb and Cd is a heterogeneous diffusion process, and the elution process is controlled by diffusion factors. After leaching with SAS-nZVI-CA, the physical and chemical properties of the soil changed little, the mobility and toxicity of HMs in the soil were reduced, and the HMs content in the leaching waste liquid was reduced. It can be concluded that SAS-nZVI enhances the efficiency of CA in extracting Pb and Cd from soil, minimizes soil damage resulting from chemical leaching technology, and alleviates the challenges associated with treating leaching waste liquid.

Green low-cost synthesis of zero-valent iron nanoparticles from Palm Petiole Extract for Cr(VI) removal from water.

One of the hottest research topics over the last decades was the valorization or/and recycling of agro-industrial wastes into different valuable liquid or solid products, which is considered a sustainable and low-cost approach. In this study, we developed zero-valent iron nanoparticles from Palm Petiole Extract (P-NZVI) using a green and straightforward approach. The as-synthesized P-NZVI was used to adsorb Cr(VI) in water. The physico-chemical characterizations of P-NZVI, including the particle size, crystalline structure, surface area, morphology, and functional groups, were investigated via several techniques such as UV-vis spectroscopy, SEM, TEM, XRD, FTIR, AFM, DLS, pHZPC measurement, and BET analysis. The adsorption performance of P-NZVI was studied under different operational parameters, including pollutant concentration, pH, temperature, and adsorbent mass. The adsorption rate was found to be 89.3% within 40 min, corresponding to the adsorption capacity of 44.47 mg/g under the following conditions: initial Cr(VI) concentration of 40 mg/L, pH 5, and a P-NZVI dosage of 1 g/L. It was found that the adsorption pattern follows the Langmuir and the pseudo-second-order kinetic models, indicating a combination of monolayer adsorption and chemisorption mechanisms. The thermodynamic study shows that the adsorption process is endothermic and spontaneous. The reusability of P-NZVI was carried out four times, showing a slight decrease from 89.3 to 87%. These findings highlight that P-NZVI's could be an effective green adsorbent for removing Cr(VI) or other types of toxic pollutants from water.

Enhanced Adsorptivity of Hexavalent Chromium in Aqueous Solutions Using CTS@nZVI Modified Wheat Straw-Derived Porous Carbon.

Using KOH-modified wheat straw as the precursor, wheat straw biochar was produced through carbonization at 500 °C. Subsequently, a synthetic material containing nano-zero-valent iron (nZVI) was prepared via liquid phase reduction (nZVI-WSPC). To enhance its properties, chitosan (CTS) was used by crosslinking to form the new adsorbent named CTS@nZVI-WSPC. The impact of CTS on parameters such as mass ratio, initial pH value, and adsorbent dosage on the adsorption efficiency of Cr(VI) in solution was investigated through one-factor experiments. Isotherm adsorption and thermodynamic analysis demonstrated that the adsorption of Cr(VI) by CTS@nZVI-WSPC conforms to the Langmuir model, with a maximum adsorption capacity of 147.93 mg/g, and the adsorption process is endothermic. Kinetic analysis revealed that the adsorption process follows a pseudo-second-order kinetic model. The adsorption mechanism, as elucidated by SEM, FTIR, XPS, and XRD, suggests that the process may involve multiple mechanisms, including pore adsorption, electrostatic adsorption, chemical reduction, and surface chelation. The adsorption capacity of Cr(VI) by CTS@nZVI-WSPC remains high after five cycles. The adsorbent is simple to operate, economical, efficient, and reusable, making it a promising candidate for the treatment of Cr(VI) in water.

The impact of heteroaggregation between nZVI and SNPs on the co-transport of Cd(II) in saturated sand columns.

This study investigated the co-transport behaviors of nano zero-valent iron (nZVI) and Cd(II) in the presence of soil nanoparticles (SNPs) under various SNPs/nZVI mass ratios. It was illustrated that the mobility of colloidal Cd(II) was highly dependent on the nZVI-SNPs heteroaggregation behavior. In the case of 40 mg/L nZVI with SNPs/nZVI mass ratios > 1, the formation of stable SNPs-nZVI heteroaggregates with hydrodynamic diameters (Dh) < 500 nm facilitated the nZVI and colloidal Cd(II) transport at their effluent mass recoveries of 34.76-37.82 % and 9.81-17.17 %, respectively. However, in the case of 100 mg/L nZVI with SNPs/nZVI mass ratios of 0.4-2, the interception of nZVI-SNPs heteroaggregates with Dh > 1500 nm by quartz sands led to almost complete retention of nZVI and colloidal Cd(II) in the columns. Combined with analytical results of zeta potentials and XRD spectrum, it was revealed that the Cd(II) ions could accelerate nZVI corrosion. The positively charged Fe3O4 and γ-FeOOH on corroded nZVI surface could facilitate the heteroaggregation of nZVI-SNPs by the patch-charge attraction, which further reduced the environmental risk of colloidal Cd(II) transport. These findings revealed the important effects of heteroaggregation between nZVI and SNPs on the transport risk of Cd(II) in groundwater.

Modified zero-valent iron nanoparticles enhanced remediation of PCBs-contaminated soil.

The high toxicity and persistence of polychlorinated biphenyls (PCBs) in the environment require effective remediation of PCBs-contaminated soil. This study used polylactic acid (PLA) and polyethylene glycol 4000 (PEG-4000) to modify zero-valent iron nanoparticles (nZVI) and conducted characterization analysis. It was found that when the addition amount of PLA was 2 %, the dispersion of modified nZVI was better. The initial pH and water to soil ratio were subjected to single factor experiments and fitted using RSM response surface methodology. The optimal reaction conditions were obtained as follows: the addition amount was 84 g·kg-1, the initial pH was 5.41, and the optimal removal rate was 74 % when the ratio of water to soil was 1.8:1. PLA and PEG-4000 were biodegradable substances that played crucial roles in enhancing the effectiveness of nZVI for PCBs-contaminated soil. By encapsulating nZVI with PLA, we significantly reduced its oxidation when exposed to air. Additionally, the inclusion of PEG-4000 helped prevent the particles from clumping together. The synergistic effect of them increased the effective reaction of nZVI and PCBs and ultimately leading to more efficient remediation. This study offered a new pathway for the efficient green remediation of PCBs-contaminated soil.

Integrated influence of sulfide modification on the reactivity of nanoscale zero-valent iron towards decabromodiphenyl ether under an electromagnetic field.

Individual application of sulfide modification and electromagnetic field (EMF) can enhance the reactivity of nanoscale zero-valent iron (nZVI), yet the potential of both in combination is not clear. This work found that the reactivity of nZVI towards decabromodiphenyl ether was significantly enhanced by the combined effect of sulfidation and EMF. The specific reaction rate constant of nZVI increased by 7 to 10 times. A series of characterization results revealed that the sulfidation level not only affects the inherent reactivity but also the magnetic-induced heating (MIH) and corrosion (MIC) of nZVI. These collectively influence the degradation efficiency of nZVI under EMF. Sulfidation generally diminished the MIH effect. The low degree of sulfidation (S/Fe = 0.1) slightly reduced the MIC effect by 21.4%. However, the high degree of sulfidation (S/Fe = 0.4) led to significantly enhanced MIC effect by 107.1%. For S/Fe = 0.1 and 0.4, the overall enhancement in the reactivity resulting from EMF was alternately dominated by the contributions of MIH and MIC. This work provides valuable insights into the MIH and MIC effects about the sulfidation level of nZVI, which is needed for further exploration and optimization of this combined technology.

In-depth understanding of transport behavior of sulfided nano zerovalent iron/reduced graphene oxide@guar gum slurry: Stability and mobility.

Nanoscale zero-valent iron (NZVI), which has the advantages of small particle size, large specific surface area, and high reactivity, is often injected into contaminated aquifers in the form of slurry. However, the prone to passivation and agglomeration as well as poor stability and mobility of NZVI limit the further application of this technology in fields. Therefore, sulfided NZVI loaded on reduced graphene oxide (S-NZVI/rGO) and guar gum (GG) with shear-thinning properties as stabilizers were used to synthesize S-NZVI/rGO@GG slurries. SEM, TEM, and FT-IR confirmed that the dispersion and anti-passivation of NZVI were optimized in the coupled system. The stability and mobility of the slurry were improved by increasing the GG concentration, enhancing the pH, and decreasing the ionic strength and the presence of Ca2+ ions, respectively. A modified advection-dispersion equation (ADE) was used to simulate the transport experiments considering the strain and physicochemical deposition/release. Meanwhile, colloidal filtration theory (CFT) demonstrated that Brownian motion plays a dominant role in the migration of S-NZVI/rGO@GG slurry, and the maximum migration distance can be increased by appropriately increasing the injection rate. Extended-Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory showed that the excellent stability and migration of S-NZVI/rGO@GG slurry mainly came from the GG spatial forces. This study has important implications for the field injection of S-NZVI/rGO@GG slurry. According to the injection parameters, the injection range of S-NZVI/rGO@GG slurry is effectively controlled, which lays the foundation for the promotion of application in actual fields.

Effect of Stabilized nZVI Nanoparticles on the Reduction and Immobilization of Cr in Contaminated Soil: Column Experiment and Transport Modeling.

Batch and transport experiments were used to investigate the remediation of loamy sand soil contaminated with Cr(VI) using zero-valent iron nanoparticles (nZVI) stabilized by carboxymethylcellulose (CMC-nZVI). The effect of pH, ionic strength (IS), and flow rate on the removal efficiency of Cr(VI) were investigated under equilibrium (uniform transport) and non-equilibrium (two-site sorption) transport using the Hydrus-1D model. The overall removal efficiency ranged from 70 to over 90% based on the chemical characteristics of the CMC-nZVI suspension and the transport conditions. The concentration and pH of the CMC-nZVI suspension had the most significant effect on the removal efficiency and transport of Cr(VI) in the soil. The average removal efficiency of Cr(VI) was increased from 24.1 to 75.5% when the concentration of CMC-nZVI nanoparticles was increased from 10 to 250 mg L-1, mainly because of the increased total surface area at a larger particle concentration. Batch experiments showed that the removal efficiency of Cr(VI) was much larger under acidic conditions. The average removal efficiency of Cr(VI) reached 90.1 and 60.5% at pH 5 and 7, respectively. The two-site sorption model described (r2 = 0.96-0.98) the transport of Cr(VI) in soil quite well as compared to the uniform transport model (r2 = 0.81-0.98). The average retardation of Cr(VI) was 3.51 and 1.61 at pH 5 and 7, respectively, indicating earlier arrival for the breakthrough curves and a shorter time to reach maximum relative concentration at lower pH. The methodology presented in this study, combining column experiment and modeling transport using the Hydrus-1D model, successfully assessed the removal of Cr(VI) from polluted soils, offering innovative, cost-effective, and environmentally friendly remediation methodologies.

Carbothermal synthesis of sulfurized nano zero-valent iron from sulfate-reducing bacteria biomass for mercury removal: The first application of biomass sulfur source.

The development of low-cost, highly efficient adsorbent materials is of significant importance for environmental remediation. In this study, a novel material, sulfurized nano zero-valent iron loaded biomass carbon (S-nZVI/BC), was successfully synthesized by a simple manufacturing process. The preparation of S-nZVI/BC does not require the use of expensive and hazardous chemicals. Instead, residual sludge, a solid waste product, is used as feedstock. The sludge is rich in Sulfate-Reducing Bacteria (SRB), which can provide carbon and sulfur sources for the synthesis of S-nZVI/BC. It was observed that S-nZVI particles formed in situ were dispersed within BC and covered by it. Additionally, S-nZVI/BC inherited the large specific surface area and porosity of BC. The adsorption capacity of S-nZVI/BC can reach 857.55 mg g-1 Hg (II) during the remediation of mercury-polluted water. This research offers new perspectives for developing composites in terms of the low cost and harmlessness of raw materials.

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.

Core to concept: synthesis, structure, and reactivity of nanoscale zero-valent iron (NZVI) for wastewater remediation.

Numerous technological advancements have been developed to tackle the issue of wastewater remediation effectively. However, the practical application of these technologies on a large scale has faced several challenges that have hindered their progress. These challenges include low selectivity, high energy requirements, and significant expenses. Nanoscale materials have demonstrated remarkable effectiveness in removing a wide range of contaminants. Nanoscale zero-valent iron (NZVI) exhibits a range of distinctive physical and chemical properties that have proven to be highly effective in various environmental remediation applications. These include its impressive surface area, remarkable reactivity, and its capacity to create stable colloidal suspensions. The paper explores the synthetic techniques for NZVI with special emphasis on green synthesis and the use of capping or support agents for maintaining stability and enhancing the reactivity of NZVI. The various structural and reactivity aspects of NZVI have been highlighted for its potential application in wastewater treatment sequestrating various categories of inorganic and organic contaminants. The discussion also delves into the limitations of NZVI, highlighting its dependence on water as a medium for contact reaction or electron transfer through the action mechanism of NZVI in adsorptive and photocatalytic sequestration of contaminants. The beneficial potential of NZVI-based composite systems in the field of environmental remediation has also been included which aids in the application of NZVI in environmental remediation.

Fast and efficient As(III) removal from water by bifunctional nZVI@NBC.

As a notable toxic substance, metalloid arsenic (As) widely exists in water body and drinking As-contaminated water for an extended period of time can result in serious health concerns. Here, the performance of nanoscale zero-valent iron (nZVI) modified N-doped biochar (NBC) composites (nZVI@NBC) activated peroxydisulfate (PDS) for As(III) removal was investigated. The removal efficiencies of As(III) with initial concentration ranging from 50 to 1000 µg/L were above 99% (the residual total arsenic below 10 µg/L, satisfying the contaminant limit for arsenic in drinking water) within 10 min by nZVI@NBC (0.2 g/L)/PDS (100 µM). As(III) removal efficiency influenced by reaction time, PDS dosage, initial concentration, pH, co-existing ions, and natural organic matter in nZVI@NBC/PDS system were investigated. The nZVI@NBC composite is magnetic and could be conveniently collected from aqueous solutions. In practical applications, nZVI@NBC/PDS has more than 99% As(III) removal efficiency in various water bodies (such as deionized water, piped water, river water, and lake water) under optimized operation parameters. Radical quenching and EPR analysis revealed that SO4·- and ·OH play important roles in nZVI@NBC/PDS system, and the possible reaction mechanism was further proposed. These results suggest that nZVI@NBC activated peroxydisulfate may be an efficient and fast approach for the removal of water contaminated with As(III).

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.

Activation of persulfate by g-C3N4/nZVI@SBC for degradation of total petroleum hydrocarbon in groundwater.

In this study, we synthesized a high removal efficiency catalyst using biochar-supported nanoscale zero-valent iron and g-C3N4, denoted as g-C3N4/nZVI@SBC, to activate persulfate (PS) for the degradation of total petroleum hydrocarbon (TPH) in groundwater. We characterized the morphology and physiochemical properties of g-C3N4/nZVI@SBC with scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform infrared (FTIR), BET surface area analysis, and X-ray photoelectron spectroscopy (XPS). To assess the performance of the g-C3N4/nZVI@SBC catalyst, we investigated various reaction parameters, such as the mass ratio of g-C3N4 to nZVI@SBC, PS concentration, initial pH, initial TPH concentration, and the presence of coexisting ions in the system. The results from batch experiments and repeated use trials indicate that g-C3N4/nZVI@SBC exhibited both excellent catalytic activation capability and impressive durability, making it a promising choice for TPH degradation. Specifically, when the PS concentration reached 1 mM, the catalyst dosage was 0.3 g/L, and the g-C3N4 to nZVI@SBC mass ratio was 2, we achieved a remarkable TPH removal efficiency of 93.8%. Through electron paramagnetic resonance (EPR) testing and quenching experiments, we identified sulfate radicals, hydroxyl radicals, and superoxide radicals as the primary active substance involved in the TPH degradation process. Moreover, the g-C3N4/nZVI@SBC composite proved highly effective for in-situ TPH removal from groundwater and displayed an 86% removal rate, making it a valuable candidate for applications in permeable reactive barriers (PRB) aimed at enhancing environmental remediation. In summary, by skillfully utilizing g-C3N4/nZVI@SBC, this study has made notable advancements in synthesis and characterization, presenting a feasible and innovative approach to addressing TPH pollution in groundwater.

Removal of dyes from wastewater using Eucalyptus wood fiber loaded nanoscale zero-valent iron: Characterization and removal mechanism.

Wood fiber as a natural and renewable material has low cost and plenty of functional groups, which owns the ability to adsorb dyes. In order to improve the application performance of wood fiber in dye-pollution wastewater, Eucalyptus wood fiber loaded nanoscale zero-valent iron (EWF-nZVI) was developed to give EWF magnetism and the ability to degrade dyes. EWF-nZVI was characterized via FTIR, XRD, zeta potential, VSM, SEM-EDS and XPS. Results showed that EWF-nZVI owned a strong magnetism of 96.51 emu/g. The dye removal process of EWF-nZVI was more in line with the pseudo-second-order kinetics model. In addition, the Langmuir isotherm model fitting results showed that the maximum removal capacities of Congo red and Rhodamine B by EWF-nZVI were 714.29 mg/g and 68.49 mg/g at 328 K, respectively. After five adsorption-desorption cycles, the regeneration efficiencies of Congo red and Rhodamine B were 74 % and 42 % in turn. The dye removal mechanisms of EWF-nZVI included redox degradation (Congo red and Rhodamine B) and electrostatic adsorption (Congo red). In summary, EWF-nZVI is a promising biomass-based material with high dye removal capacities. This work is beneficial to promote the large-scale application of wood fiber in water treatment.

Catalytic activation of persulfate by nanoscale zero-valent iron-derived supported boron-doped porous carbon for bisphenol A degradation.

In this study, boron-doped porous carbon materials (BCs) with high surface areas were synthesized employing coffee grounds as carbon source and sodium bicarbonate and boric acid as precursors; afterward, nanoscale zero-valent iron (nZVI) and BCs composites (denoted as nZVI@BCs) were further prepared through reduction of FeSO4 by NaBH4 along with stirring. The performance of the nZVI@BCs for activating persulfate (PS) was evaluated for the degradation of bisphenol A (BPA). In comparison with nZVI@Cs/PS, nZVI@BCs/PS could greatly promote the degradation and mineralization of BPA via both radical and non-radical pathways. On the one hand, electron spin resonance and radical quenching studies represented that •OH, SO4•-, and O2•- were mainly produced in the nZVI@BCs/PS system for BPA degradation. On the other hand, the open circuit voltages of nZVI@BCs and nZVI@Cs in different systems indicated that non-radical pathway still existed in our system. PS could grab the unstable unpaired electron on nZVI@BCs to form a carbon material surface-confined complex ([nZVI@BCs]*) with a high redox potential, then accelerate BPA removal efficiency via direct electron transfer. Furthermore, the performances and mechanisms for BPA degradation were examined by PS activation with nZVI@BC composites at various conditions including dosages of nZVI@BCs, BPA and PS, initially pH value, temperature, common anions, and humid acid. Therefore, this study provides a novel insight for development of high-performance carbon catalysts toward environmental remediation.