Zero-valent Iron Research Articles

Investigation of small-strain shear modulus of marine sediment treated with different flocculants

Dredged sediments are typically found near coastal areas. Because of its high compressibility potential and low strength, multiple studies have tested various substances that can be mixed with the dredged materials to enhance the overall treatment process while minimizing post-construction settlement. Recent investigations indicated that combining flocculants such as cationic polyacrylamide (CPAM) with marine sediment improves the consolidation and permeability properties compared to untreated soil. Despite its importance, only a few studies have focused on the mechanical properties of marine sediment treated with various flocculant types. This study employs a bender element apparatus to examine the small-strain shear modulus (Gmax) variation of Macau marine sediment treated with three different flocculants: CPAM; chitosan; and nanoscale zero-valent iron (nZVI). The result revealed that the Gmax of natural marine sediment increases when blended with chitosan and CPAM with medium cationicity. Interestingly, no apparent change in Gmax values was observed when the marine sediment samples were treated using CPAM with high cationicity. In contrast, the Gmax values of soil samples treated with nZVI decreased. The comparison with existing empirical models reveals that the plasticity index is a significant parameter in determining the Gmax of Macau marine sediments. The findings from this study will support the identification of viable filling materials for future land reclamation projects in the Greater Bay Area of China.

ZVI-biochar granules for reactive chlorinated solvent filters generated by high temperature pyrolysis of iron(III) amended biomass

Reactive filters may replace activated carbon filters for degradation of chlorinated solvents in contaminated waters. Reactive porous filter materials with high hydraulic conductivity may be in form of millimeter sized zero valent iron (ZVI)-biochar granules produced via carbothermal reduction. We screened ZVI-biochar materials produced under different synthesis conditions including different iron sources, nitrogen additives and supplementary organic substrates followed by testing adsorption and dechlorination kinetics. Diatomaceous earth was used as an inorganic host reference material. The optimal product from the screening was identified as beech charcoal amended with Fe(III) chloride and urea followed by tube furnace pyrolysis at 1000 °C for 2 h. The millimeter sized granules have a high porosity of 79 %. This material resulted in fast trichloroethylene (TCE, 100–600 µM) sorption and complete dechlorination with acetylene as the main product. It also showed a 5 to 8.5-fold higher degradation capacity than the diatomaceous earth reference system. Fitted pseudo first-order dechlorination rate constants (0.114–0.281 h−1) were comparable to rates reported for powdered ZVI-activated carbon materials. In reactions with high TCE concentrations, Fe(0) consumption for TCE reduction reached up to 93.3 % demonstrating its high selectivity. Reactions with ground material demonstrated that intraparticle diffusion pose minor limitation to dehalogenation rates in the highly porous granules. Further tests demonstrated that the material was further highly reactive to tetrachloroethylene (PCE), cis-1,2-dichloroethyene (cis-DCE) and vinyl chloride (VC). The ZVI-BC material addresses the dual challenges of achieving both high hydraulic conductivity and dehalogenation reactivity, offering a cost-efficient and sustainable option for filter material selection in the remediation of CEs using reactive filters or permeable reactive barriers.

Sulfidation of air-stable iron nanoparticles: A novel strategy how to boost their reactivity demonstrated on Cr(VI) reduction

Sulfidated zero-valent iron nanoparticles (S-nZVI) have been extensively studied as environmentally promising alternative material, which enables reduction of variety of extremely dangerous pollutants directly in the environment. However, synthesis and manipulation with these extremely reactive/pyrophoric nZVI particles represents a challenge and requires special precautions. In this study, we report a synthesis of S-nZVI from air-stable core-shell nZVI, which reactivity with contaminants and properties are comparable with the commonly prepared S-nZVI particles (where the precursor was bare/pyrophoric nZVI particles). The undeniable novelty dwells in the simplicity of the synthetic process, which ensures consequential safe and easy handling, manipulation, and application of S-nZVI particles. This material, especially highly effective against halogenated organic compounds and heavy metals, was characterized in detail and its advanced characteristics were evaluated in the process of hexavalent chromium (Cr(VI)) reduction from model aqueous solutions and polluted groundwater. The results offer valuable insights into the preparation of a novel nanomaterial with high application potential in the effective degradation of heavy metals in polluted water. Overall, the novel way prepared S-nZVI particles, designed for the potential large-scale production, eliminates the drawbacks of S-nZVI synthesized from bare nZVI particles and offers the effective material suitable for any on-site application.

Synergetic effect of pyrrhotite and zero-valent iron on Hg(Ⅱ) removal in constructed wetland: Mechanisms of electron transfer and microbial reaction

Effective removal of mercury (Hg) from wastewater is significant due to its high toxicity, especially methylmercury (MeHg). Reducing of Hg(II) to Hg(0) in constructed wetlands (CWs) using iron-based materials is an effective strategy for preventing the formation of MeHg. However, the surface passivation of zero-valent iron (ZVI) limits its application. Herein, synergetic ZVI and pyrrhotite were utilized to enhance Hg removal in CWs. Results indicated that the removal of total Hg, dissolved Hg, and particulate Hg in CWs with ZVI and pyrrhotite were improved by 21.68 ± 0.76 %, 13.02 ± 0.88 %, and 22.27 ± 0.76 % compared to that with single ZVI or pyrrhotite. Pyrrhotite increased the surface corrosion of ZVI, thereby facilitating the process of iron reduction. The redox of iron promoted the generation of EPS, which could provide electrons for Hg(II) reduction. The sulfur also participates in electron transfer by driving the methylation of Hg and provides sulfides to form FeS-Hg complexes and HgS precipitation. The abundance of key enzymes that involved in iron reduction and Hg transformation was enhanced with the addition of ZVI and pyrrhotite. The synergetic of pyrrhotite and ZVI enhances the removal of Hg in CW, offering a promising technology for high-efficiency treatment of Hg.

The Application of Nano Zero-Valent Iron in Synergy with White Rot Fungi in Environmental Pollution Control.

Developing efficient and sustainable pollution control technologies has become a research priority in the context of escalating global environmental pollution. Nano zero-valent iron (nZVI), with its high specific surface area and strong reducing power, demonstrates remarkable performance in pollutant removal. Still, its application is limited by issues such as oxidation, passivation, and particle aggregation. White rot fungi (WRF) possess a unique enzyme system that enables them to degrade a wide range of pollutants effectively, yet they face challenges such as long degradation cycles and low degradation efficiency. Despite the significant role of nZVI in pollutant remediation, most contaminated sites still rely on microbial remediation as a concurrent or ultimate treatment method to achieve remediation goals. The synergistic combination of nZVI and WRF can leverage their respective advantages, thereby enhancing pollution control efficiency. This paper reviews the mechanisms, advantages, and disadvantages of nZVI and WRF in pollution control, lists application examples, and discusses their synergistic application in pollution control, highlighting their potential in pollutant remediation and providing new insights for combined pollutant treatment. However, research on the combined use of nZVI and WRF for pollutant remediation is still relatively scarce, necessitating a deeper understanding of their synergistic potential and further exploration of their cooperative interactions.

Zero-valent iron on graphite-cellulose biochar catalysts for the Fenton degradation of tetracycline from water

Tetracycline (TC), an antibiotic widely used in the treatment of animal and human diseases and promotion of animal growth. However, its uncontrolled discharge to water sources can also cause the promotion of antibiotic resistant bacteria and genes. In this study, graphite and cellulose were used as raw materials to construct a graphite-biochar (G-BC) by carbothermal reactions. This graphite-biochar was subsequently mixed with ZVI with various mass ratios by ball milling to produce graphite-biochars supported ZVI (ZVI/G-BC) catalysts, further used in the heterogeneous Fenton degradation of tetracycline. The materials were fully characterized by different techniques. The removal of TC by BC, G-BC and ZVI/G-BC was tested under different reaction conditions. The best synthesis conditions were achieved at a heating temperature of 700 °C, a graphite content of 20 %, a ball milling speed of 500 rpm, a ball milling time of 5 h, as well as a G-BC and ZVI mass ratio of 1:3. Graphite improves the conductivity and micropore area of the material, which enhances the removal of TC by ZVI/G-BC catalysts in Fenton-like reactions. TC was first oxidized to intermediate products and then further mineralized to CO2 and H2O. The best TC removal performance was obtained with a catalyst dosage of 1.1 g·L1, a hydrogen peroxide concentration of 140 mM and an initial pH value of 3. The reaction data fitted properly a pseudo first-order kinetic equation. TC removal as high as 91 % was achieved even in the 3rd round of reuse. This study reports a novel ZVI material with high conductivity and good TC removal performance.

In situ treatment of contaminated soil using persulfate activated by sulfidated zero-valent iron

Soil contamination with hazardous substances like phenol poses significant environmental and health risks. In situ soil mixing can be a promising technological solution to this challenge. A persulfate and sulfidated zero-valent iron (S-ZVIbm) system for remediating contaminated soil was developed and tested to be suited to in situ soil mixing. S-ZVIbm was synthesized using a ball mill process, and the optimal sulfur to iron molar ratio for effectively removing phenol from soil removal without pyrophoric risks was 0.12. Soil slurry experiments were performed, and the best phenol oxidation results (high stoichiometric efficiency and sustained oxidation after mixing) were achieved at a persulfate to S-ZVIbm molar ratio of 2:1 and a persulfate to phenol molar ratio of 8:1. A high organic matter content of the silty clay fraction of the soil strongly suppressed persulfate activation, so suppressed phenol removal and increased persulfate consumption. Electron spin resonance and radical scavenging tests confirmed that hydroxyl and sulfate radicals were present during the degradation of phenol. While sulfate radicals predominantly facilitated degradation in the soil, both sulfate and hydroxyl radicals were crucial in the aqueous phase in the absence of soil organic matter. In situ soil mixing simulation tests indicated that the persulfate and S-ZVIbm doses and the mixing rate and duration strongly affected the efficacy of the system, and the optimal conditions for phenol removal were determined. The results indicated that the persulfate/S-ZVIbm system could be tuned to achieve sustained persulfate activation and to remediate contaminated soil employing in situ soil mixing technique.

Synergistic adsorption and degradation of sulfonylurea herbicides by biochar-supported nano zero-valent iron composites in in-situ soil remediation

The extensive and continuous application of sulfonylurea herbicide is crucial for weed management but has resulted in widespread non-point source pollution. In this study, nano zero-valent iron/biochar (nZVI/BC) was synthesized by using FeCl3-impregnated corn stalks under anoxic pyrolysis conditions, which was applied in the in-situ remediation of bensulfuron methyl (BSFM) and sulfometuron methyl (SMTM) polluted soil. The results show that nZVI/BC with a 2.7 ratio of Fe/C had the highest efficiency in removing sulfonylurea herbicides. The removal efficiencies of BSFM and SMTM by nZVI/BC were negatively correlated to initial concentrations of sulfonylurea herbicides and positively correlated to nZVI/BC addition amount in the soil. Moreover, nZVI/BC could remove 53 % of BSFM and 72 % of SMTM at the concentration of 5 mg/kg after 21 d, which was much higher than that of BC. Notably, the removal efficiency of BSFM by nZVI/BC reached 36 % within 7 d, while the removal efficiency of SMTM by nZVI/BC was up to 68 % even within 3 d. The adsorption of herbicides by nZVI/BC was mainly driven by chemical processes involving multilayer adsorption. Furthermore, the removal mechanisms of BMTM and SMTM by nZVI/BC also involved C = O and C–O groups and oxidation of nZVI to FeO and Fe3O4 along with the cleavage of the sulfonylurea bridge. This study provides a promising application of nZVI/BC in in-situ remediating sulfonylurea herbicide- polluted soil.

Effective removal of nitrate by palygorskite-supported nanoscale zero-valent iron from aqueous solution

Nitrate nitrogen (NO3--N) has become an important pollutant in industrial and agricultural production processes in China. In this study, Palygorskite-supported nanoscale zero-valent iron (nZVI/PG) adsorbent was prepared using the liquid-phase reduction method for the removal of NO3--N from water. Benefiting from the good dispersion uniformity of nZVI on the Palygorskite carrier, the prepared nZVI/PG exhibited a significantly increased specific surface area compared to nZVI, with a noticeable reduction in nZVI aggregation. The Fe/PG mass ratio of 2:1 was found to be the optimal loading ratio for the removal of NO3--N by nZVI/PG, with a removal capacity of 24.36 mg/g and a removal efficiency of 81.23 %, with a nitrogen gas conversion rate of 40.92 %. The removal process of NO3--N by nZVI/PG followed a pseudo-second-order kinetic model, with the removal rate inversely proportional to the initial concentration of NO3--N and directly proportional to the dosage. nZVI/PG exhibited high removal efficiency for NO3--N within the pH range of 2 to 9, with the highest selectivity for NO3--N conversion to N2 observed at pH 5. The main mechanism for the removal of NO3--N by nZVI/PG was found to be adsorption and reduction, with the main products being NH4+-N, NO2--N, and N2.

Time-dependent redistribution of soil arsenic induced by transformation of iron species during zero-valent iron biochar composites amendment: Effects on the bioaccessibility of As in soils

Zero-valent iron biochar composites (ZVI/BC) are considered as effective amendments for arsenic (As)-contaminated soils. However, the mechanisms of transformation of various soil As species during ZVI/BC amendments remain unclear. This study investigated As transformation in four soils (namely, GX, ZJ, HB, and HN) treated with ZVI/BC for 65 days under two soil moisture conditions, unsaturated and oversaturated. Results showed that the 65-day treatment was divided into two stages based on the variation of labile As content. Within 2 days (stage 1), ZVI/BC addition quickly reduced labile As content by 5.91–90.3 % in soils under unsaturated conditions. During days 2–65 (stage 2), labile As ultimately decreased by 0.06–0.31 mg/kg in GX, ZJ, and HB while increasing by 22.1 mg/kg in HN soil, due to its lower pH value and Fe content. The variations of labile As were attributed to changes in multiple Fe minerals and associated As species. In stage 1, the corrosion of ZVI/BC generated amorphous Fe oxides to immobilize labile As, resulting in the accumulation of meta-stable As. In stage 2, amorphous Fe oxides were transformed into crystalline Fe oxides, resulting in the release and re-precipitation of As along with transformation, thus redistributing immobilized As into labile and stable As, which was evidenced by multiple methods, including chemical extraction, XRD, and TEM-EDX. The elevated soil moisture condition would enhance the corrosion of ZVI/BC in stage 1, further forming a reductive environment to facilitate the transformation of Fe minerals in stage 2. Besides, As bioaccessibility in soils was reduced by 10.8–38.7 % after ZVI/BC treatment in in-vitro gastrointestinal simulations. Overall, our study revealed the time-dependent transformation mechanism of soil As species and associated Fe minerals under different soil moisture with ZVI/BC treatments, and highlighted the effectiveness of ZVI/BC as a long-term amendment for As-contaminated soils.

ZnO/nZVI nanoparticle-enhanced double-slope U-shaped solar distillation: A thermodynamic investigation of cephalexin adsorption

The increasing need for sustainable methods to remove pharmaceutical contaminants like cephalexin and improve water desalination is critical. This study explores ZnO/nZVI nanoparticles synthesized with Jackfruit peel extracts as eco-friendly, cost-effective adsorbents, enhancing water purification in solar desalination systems. This work used a matte black paint coating within a double slope U-shaped solar distiller (DSUD) in a discontinuous experimental setting to examine potential improvements in solar distillation performance. Activated carbon (AC) and bioactive powdered nanoparticles of ZnO/nZVI (nano zerovalent iron), produced from jackfruit peel extracts (JP) were combined in a synergistic way. The effectiveness of cephalexin removal was assessed taking into account the JPAC solution parameters, reaction duration, ZnO/nZVI concentrations in the nanocomposite dosage, and initial nanocomposite concentration. The best conditions for cephalexin adsorption were found to be pH 5 and reaction time of 50 min, which resulted in high absorption efficiencies of 94.74% (nZVI) and 97.53% (ZnO) at room temperature with a JPAC dose of 2.50 g L⁻1. The efficiency of the eco-friendly adsorbent in getting rid of cephalexin was calculated using “pseudo-second-order kinetics” for nanocomposites, which is consistent with the “Langmuir” isothermal absorption process. The nanocomposites as absorbent materials in solar thermal desalination processes, efficient heat transmission and energy storage have been established. JPAC and the addition of steel balls (S) with a silver hue to the DSUD improved the internal heat transfer mechanisms. Thermodynamic of Gibbs free energy and the Laplacian method (TGL), two thermodynamic concepts, were used to extensively study the temperature dynamics of the DSUD with SJPAC components. For ZnO/JPAC, an exceptional distillate production rate was noted from 8:00 to 18:00, with a noteworthy 4.932 L/m2 output in winter and 5.833 L/m2 per day in summer. Using silver balls, ZnO/JPAC generated significant yields over a 24-h period: 8.957 L/m2 in summer and 7.253 L/m2 in winter, with an ideal energy efficiency of 51.05%. The unique advancements in TGL procedures and their environmental consequences are presented in this paper. The field of thermal energy transduction will advance if silver balls are used in DSUD for the synthesis of JPAC, ZnO/JPAC, and nZVI/JPAC, as supported by the theoretical insights presented here.

New insights on zero-valent iron permeable reactive barrier for Cr(VI) removal: The function of FeS reaction zone downstream in-situ generated by sulfate-reducing bacteria

The biogeochemical behavior downstream of the zero-valent iron permeable reactive barrier (ZVI-PRB) plays an enormous positive role in the remediation of contaminated-groundwater, but has been completely neglected for a long time. Therefore, this study conducted a 240-day SRB-enhanced ZVI-PRB column experiment, focusing on what exactly happens downstream of ZVI-PRB. Results show that biosulfidation of SRB inside ZVI-PRB prolonged the complete Cr(VI) removal longevity of ZVI-PRB from 38 days to at least 240 days. More importantly, unlike previous studies that focused on improving the performance of ZVI-PRB itself, this study found an in-situ generated FeS reduction reaction zone downstream of the ZVI-PRB. When the ZVI-PRB fails, the downstream reaction zone can continue to play a role in Cr(VI) removal. The maximum Cr(VI) removal capacity of the aquifer media from the reaction zone reached 155.1mg/kg, which was 39.7% of commercial ZVI capacity. The reduction zone was further confirmed to be predominantly FeS rather than FeS2. Biogeochemistry occurring within and downstream of ZVI-PRB leads to the formation of FeS. Gene sequencing revealed significantly higher SRB abundance downstream of ZVI-PRB than within the ZVI-PRB. The understanding of the downstream FeS reaction zone provides new insights for more effective remediation using ZVI-PRB.

Degradation kinetics, influencing factors, and mechanisms of polycyclic aromatic hydrocarbons in a Fe3O4-nZVI Fenton-like system

To improve the catalytic performance of nano zero-valent iron (nZVI) in a Fenton-like system, Fe3O4 supported nZVI (Fe3O4-nZVI) was produced by the liquid-phase reduction method and co-precipitation method, then characterized by SEM, EDS, XRD, XPS, and VSM. Fe3O4-nZVI was used as the catalyst in a Fenton-like system to degrade polycyclic aromatic hydrocarbons (PAHs) such as naphthalene (Nap), phenanthrene (Phe), and pyrene (Pyr) in simulated wastewater. The results showed that under the optimization conditions, which were 25℃, 0.6g/L of Fe3O4-nZVI dosage, 3 of the pH in the reaction system, and 10-15mmol/L of the concentration of H2O2, the sequence of degradation efficiency in this system was Phe (99.76%)>Pyr (99.71%)>Nap (98.01%). The reused experiments on Fe3O4-nZVI showed that the degradation efficiency for PAHs remained above 87% after 4 reuses of Fe3O4-nZVI. These results indicated that nanoscale magnetic composites of Fe3O4-nZVI had excellent reactivity, stability, and reuse performance. The fitting parameters of kinetics showed that the degradation of PAHs in the Fenton-like system with the Fe3O4-nZVI catalyst fitted well with the Behnajady-Modirshahla-Ghanbery kinetic model. The radial quenching experiment proved that ·OH was the dominant free radical for the degradation of PAHs in the Fe3O4-nZVI Fenton-like system. Based on the degradation products of PAHs and the related literature, the possible degradation paths of the three PAHs in the Fe3O4-nZVI Fenton-like system were inferred. The above results could provide a reference and basis for the treatment of wastewater containing PAHs by Fe3O4-nZVI Fenton-like technology.

High stability and reactivity of porous calcium tartrate supported nano zero-valent iron in aerobic environment and alkaline wastewater

Nano zero-valent iron (nZVI) has remarkable reactivity, but its practical application is severely hindered by its easy aggregation and rapid oxidation after exposure in air. In this study, spherical porous calcium tartrate (CaTr) was synthesized with ultrasound technology and used to support nZVI. It was found that the as-obtained nZVI@CaTr was highly stable and reactive in oxygen-rich water under neutral/alkaline conditions. In the pH range of 4–9, the degradation efficiency of p-nitrophenol (PNP, 50 mg/L) by nZVI@CaTr7 exceeded 98.1 %. Importantly, nZVI@CaTr could be stored in air for a long time without inert gas protection. After 60 days and 120 days of air exposure, the removal efficiency of PNP still reached 83.3 % and 63.3 %, which was 2.8 and 9.7 times that of bare nZVI, respectively. Such an excellent performance could be attributed to two reasons: (i) spherical CaTr effectively inhibited the oxidation and aggregation of nZVI by favorable interactions with nZVI, and (ii) the abundant functional groups on the surface of CaTr acted as electronic mediators to significantly promote charge transfer between nZVI (electron donor) and PNP (electron acceptor). Therefore, cheap, air stable and highly effective nZVI@CaTr7 provided a potential application prospect for the degradation of environmental pollutants in aerobic environment and alkaline wastewater.

Carbothermally synthesized, lignin biochar-based, embedded and surface deposited nano zero-valent iron composites: Comparative material characterization, selective gas adsorption and nitroaromatics remediation

Biochar (BC) with nanoscale zero valent iron (nZVI) incorporation offers advantageous materials for water purification. Even though the most common approach for nZVI incorporation is the deposition on the carrier surface, embedding in the support matrix has also been reported. However, the behavior of the embedded material in contaminant removal has not been adequately studied while characteristics and the remediation capabilities of the two materials have not been compared. Present study focuses on preparing and extensively characterizing two materials: nZVI embedded in (Lig-e-nZVI) and surface deposited on (Lig-s-nZVI) lignin BC with subsequent comparative study of remedial action for two nitroaromatics, p-nitroaniline (pNA) and p-nitrophenol (pNP). The synthesis of Lig-e-nZVI and Lig-s-nZVI involved simultaneous and subsequent pyrolysis of lignin and carbothermal reduction of the iron salt, respectively. Lig-e-nZVI showed enhanced porosity. XRD confirmed the formation of Fe0. HR-TEM images proved the core-shell structure of nZVI, and an interlayer spacing of 0.36nm of the shell verified that the Fe0 particles are encapsulated with graphene while an iron carbide inner layer was also observed, thinner in Lig-e-nZVI and thicker in Lig-s-nZVI. Band gap energy of 2.54eV suggested a photocatalytic activity of both materials. Best fitted Sips isotherms showed 23.1 and 13.1mgg-1 capacities for Lig-s-nZVI in pNP and pNA adsorption respectively. Highest stability was portrayed by Lig-e-nZVI over 4 regeneration cycles. The physicochemical features of the developed materials further enable selective gas adsorption. Findings provide new insights into physicochemical characteristics and remedial actions of differently synthesized nZVI-BC composites.

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.

BioRicinus Communis Seed Extract was Used in the Green Manufacture of Zero-valent Iron Nanoparticles for Photocatalyst Elimination of Chromium

Zero-valent iron was produced in this work utilising BioRicinus communis seed extract. XRD, SEM, and TEM methods were used to characterise the physicochemical characteristics of the finished products. According to TEM analysis, the iron zero-valent nanomaterials with diameters ranging from 20 to 40 nm and shell-core architectures were successfully produced. XRD findings verified the existence of several organic compounds. The photoactivity of the product was investigated by reducing the contaminant. According to the test result, the inclusion of fruit extract as a nanoscale catalyst in the photocatalyst reduced the hexavalent chromium. According to photocatalyst results, when the particulate dose was 0.675 g/L, the trivalent chromium suffered from low was 100%. A pseudo-second-order solution describes this reaction's kinetics. At pH 3 and 0.5 g/L seed extract concentration, the kinetic rate constant is 0.4. As a result, the frequency of the photocatalyst was significantly increased, and a more significant amount of Cr (VI) was eliminated. The accessible sites became progressively constrained and overloaded with bichromate particles as the starting content of Cr (VI) was increased at a consistent dose. Changing the nanoparticle dosage may considerably boost the reaction rate, hence the effectiveness of a photocatalyst's Cr (VI) catalytic cycle.

Mechanochemical Thioglycolate Modification of Microscale Zero-Valent Iron for Superior Heavy Metal Removal.

Microscale zero-valent iron (mZVI) is widely used for water pollutant control and environmental remediation, yet its reactivity is still constrained by the inert oxide shell. Herein, we demonstrate that mechanochemical thioglycolate (TG) modification can dramatically enhance heavy metal (NiII, CrVI, CdII, PbII, HgII, and SbIII) removal rates of mZVI by times of 16.7 to 88.0. Compared with conventional impregnation (wet chemical process), this dry mechanochemical process could construct more robust covalent bonding between TG and the inert oxide shell of mZVI through its electron-withdrawing carboxylate group to accelerate the electron release from the iron core, and more effectively strengthen the surface heavy metal adsorption through metal(d)-sulfur(p) orbital hybridization between its thiol group and heavy metal ions. Impressively, this mechanochemically TG-modified mZVI exhibited an unprecedented NiII removal capacity of 580.4 mg Ni g-1 Fe, 17.1 and 9.5 times those of mZVI and wet chemically TG-modified mZVI, respectively. Its application potential was further validated by more than 10 days of stable groundwater NiII removal in a column flow reactor. This study offers a promising strategy to enhance the reactivity of mZVI, and also emphasizes the importance of the modification strategy in optimizing its performance for environmental applications.

Fe (hydr)oxides and organic colloids mediate colloid-bound chromium mobilization in Cr(VI) contaminated paddy soil

The association of chromium (Cr) with colloidal particles transport in contaminated sites can affect hexavalent chromium (Cr(VI)) migration and transformation, which is an important mechanism for Cr pollutants in soil and groundwater systems. Here, we investigated colloid and particle-bound Cr migration and transformation effects on rice Cr accumulation during different rice growth stages and different redox conditions in Cr(VI) contaminated soil by pot experiment. Results showed that 13–29% of soil Cr was water dispersible colloid-bound (100–1000 nm) form during rice growth. Using transmission electron microscopy - energy dispersion spectroscopy and asymmetric flow field - flow separation, we identified colloid-bound organic matter (OM) and iron (Fe), most likely in the form of Fe (hydr)oxides - clay composites, as the primary Cr carrier. Specifically, colloid-bound Cr was mainly associated with 125–350 nm soil particle size. Under different redox conditions, colloid- and nanoparticle-bound Cr concentration decreased with increasing nanoparticles zero-valent iron (nZVI) dose. Soil reoxidation promoted the colloid- and nanoparticle-bound Cr release due to the weakly crystalline Fe-(hydr)oxides reprecipitation. Further quantitative analysis showed that colloid-bound Cr concentrations were positively correlated with colloid-bound Mn concentrations during the whole rice growth soils. Most important of all, Cr content in rice grain was positively correlated with colloid-bound Cr significantly. This study provides a quantitative and size-resolved understanding of particle-bound Cr in paddy soils, highlighting the importance of colloid-bound Cr and Fe interactions in Cr geochemical cycle of paddy soil.

Mechanisms of horizontal gene transfer and viral contribution to the fate of intracellular and extracellular antibiotic resistance genes in anaerobic digestion supplemented with conductive materials under ammonia stress

The addition of conductive materials (CMs) is an effective strategy for mitigating ammonia inhibition during anaerobic digestion (AD). However, the introduction of CMs can result in increased antibiotic resistance genes (ARGs) pollution, potentially facilitated by enhanced horizontal gene transfer (HGT). The complex dynamics of intracellular and extracellular ARGs (iARGs/eARGs) and the mechanisms underlying their transfer, mediated by CMs, in ammonia-stressed AD systems remain unclear. In this study, we investigated the effects of three commonly used CMs—nano magnetite (Mag), nano zero-valent iron (nZVI), and granular activated carbon (GAC)—on the fate of iARGs and eARGs during the AD of waste activated sludge under ammonia stress. The results revealed an unexpected enrichment of iARGs by 1.5 %–10.9 % and a reduction of eARGs by 14.1 %–25.2 % in CM-supplemented AD. This discrepancy in the dynamics of iARGs and eARGs may be attributed to changes in microbial hosts and the horizontal transfer of ARGs. Notably, CMs activated prophages within antibiotic-resistant bacteria (ARB) and their symbiotic partners involved in vitamin B12 provision, leading to the lysis of ARB and the subsequent release of eARGs for transformation. Additionally, the abundance of potentially mobile ARGs, which co-occurred with mobile genetic elements, increased by 56.6 %–134.5 % with CM addition, highlighting an enhanced potential for the HGT of ARGs. Specifically, Mag appeared to promote both transformation and conjugation processes, while nZVI only promoted conjugation. Moreover, none of the three CMs had any discernible impact on transduction. GAC proved superior to both nano Mag and nZVI in controlling the enrichment of iARGs, reducing eARGs, and limiting HGTs simultaneously. Overall, these findings provide novel insights into the role of viruses and the mechanisms of ARG spread in CM-assisted AD, offering valuable information for developing strategies to mitigate ARG pollution in practical applications.