A multiple Kirkendall strategy for converting nanosized zero-valent iron to highly active Fenton-like catalyst for organics degradation.

Nanosized zero-valent iron (nZVI) is a promising persulfate (PS) activator, however, its structurally dense oxide shell seriously inhibited electrons transfer for O-O bond cleavage of PS. Herein, we introduced sulfidation and phosphorus-doped biochar for breaking the pristine oxide shell with formation of FeS and FePO4-containing mixed shell. In this case, the faster diffusion rate of iron atoms compared to shell components triggered multiple Kirkendall effects, causing inward fluxion of vacancies with further coalescing into radial nanocracks. Exemplified by trichloroethylene (TCE) removal, such a unique "lemon-slice-like" nanocrack structure favored fast outward transfer of electrons and ferrous ions across the mixed shell to PS activation for high-efficient generation and utilization of reactive species, as evidenced by effective dechlorination (90.6%) and mineralization (85.4%) of TCE. [Formula: see text] contributed most to TCE decomposition, moreover, the SnZVI@PBC gradually became electron-deficient and thus extracted electrons from TCE with achieving nonradical-based degradation. Compared to nZVI/PS process, the SnZVI@PBC/PS system could significantly reduce catalyst dosage (87.5%) and PS amount (68.8%) to achieve nearly complete TCE degradation, and was anti-interference, stable, and pH-universal. This study advanced mechanistic understandings of multiple Kirkendall effects-triggered nanocrack formation on nZVI with corresponding rational design of Fenton-like catalysts for organics degradation.

Highly selective synthesis of surface FeIV=O with nanoscale zero-valent iron and chlorite for efficient oxygen transfer reactions.

High-valent iron-oxo species (FeIV=O) has been a long-sought-after oxygen transfer reagent in biological and catalytic chemistry but suffers from a giant challenge in its gentle and selective synthesis. Herein, we propose a new strategy to synthesize surface FeIV=O (≡FeIV=O) on nanoscale zero-valent iron (nZVI) using chlorite (ClO2-) as the oxidant, which possesses an impressive ≡FeIV=O selectivity of 99%. ≡FeIV=O can be energetically formed from the ferrous (FeII) sites on nZVI through heterolytic Cl-O bond dissociation of ClO2- via a synergistic effect between electron-donating surface ≡FeII and proximal electron-withdrawing H2O, where H2O serves as a hydrogen-bond donor to the terminal O atom of the adsorbed ClO2- thereby prompting the polarization and cleavage of Cl-O bond for the oxidation of ≡FeII toward the final formation of ≡FeIV=O. With methyl phenyl sulfoxide (PMS16O) as the probe molecule, the isotopic labeling experiment manifests an exclusive 18O transfer from Cl18O2- to PMS16O18O mediated by ≡FeIV=18O. We then showcase the versatility of ≡FeIV=O as the oxygen transfer reagent in activating the C-H bond of methane for methanol production and facilitating selective triphenylphosphine oxide synthesis with triphenylphosphine. We believe that this new ≡FeIV=O synthesis strategy possesses great potential to drive oxygen transfer for efficient high-value-added chemical synthesis.

Investigating the physicochemical, antimicrobial and antioxidant properties of chitosan film containing zero-valent iron nanoparticles and oregano essence.

The problems caused by the pollution of the environment by petroleum polymers in recent years have caused researchers to think of replacing petroleum polymers with biodegradable and natural polymers. The aim of this research was to produce composite film of chitosan (Chit)/zero-valent iron (Fe) nanoparticles/oregano essence (Ess) (Chit/Fe/Ess). Central composite design was used to study physical, morphological, antioxidant and antimicrobial properties of films. The results showed that with the increase of iron nanoparticles and oregano essence, the thickness of the film increased. The moisture, solubility and water vapor permeability of the film decreased with the increase of iron nanoparticles and oregano essence. The results of the mechanical test showed that with the increase of iron nanoparticles and oregano essence, the tensile strength and elongation at break point decreased. Iron nanoparticles and oregano essence increased significantly the antioxidant activity of the film. The results of the antimicrobial activity of the prepared films show that the addition of iron nanoparticles and oregano essence enhanced the antimicrobial activity of the film against Escherichia coli and Staphylococcus aureus. X-ray diffraction analysis showed that iron nanoparticles were physically combined with chitosan polymer. Fourier transform infrared (FTIR) results confirmed the physical presence of iron nanoparticles and oregano essence in the polymer matrix. The results of scanning electron microscopy (SEM) showed that the surface of nanocomposite films is more heterogeneous than chitosan. Iron nanoparticles and oregano essence could delay the thermal decomposition of chitosan and increase the thermal stability of chitosan film.

Metformin-modified polyethersulfone magnetic microbeads for effective arsenic removal from apatite soil leachate water.

Arsenic is the hazardous species and still is the global challenge in water treatment. Apatite soil is highly rich in arsenic species, and its mining presents various environmental issues. In this study, novel magnetic microbeads as adsorbent were developed for the elimination of hazardous arsenic ions from apatite soil's aqueous leachate before discharging into environment. The microbeads were fabricated with metformin polyether sulfone after being doped with zero-valent iron (Met-PES/ZVI). The microbeads were characterized using various techniques, including FTIR, XRD, SEM-EDX, VSM, and zeta potential analysis. The developed adsorbent demonstrated a significant elimination in arsenic in aqueous leachate, achieving 82.39% removal after 30 min of contact time, which further increased to 90% after 180 min of shaking. The kinetic analysis revealed that the pseudo-second-order model best represented the adsorption process. The intra-particle diffusion model indicated that the adsorption occurred in two steps. The Langmuir model (R2 = 0.991), with a maximum adsorption capacity of 188.679 mg g-1, was discovered to be the best fit for the experimental data as compared Freundlich model (R2 = 0.981). According to the thermodynamic outcome (ΔG < -20 kJ/mol), the adsorption process was spontaneous and involved physisorption. These findings demonstrate the potential of magnetic Met-PES/ZVI microbeads as an efficient adsorbent for the removal of arsenic from apatite soil aqueous leachate.

Application and development of zero-valent iron (ZVI)-based materials for environmental remediation: A scientometric and visualization analysis.

Zero-valent iron (ZVI)-based materials are among the most widely used engineered particles in the field of environmental remediation. To provide a comprehensive overview of the status and trend of the research on them, this study conducted a quantitative and visual analysis of 6296 relevant publications obtained from Web of Science between 1994 and 2022 using CiteSpace software. By using the bibliometric method, this work systematically analyzed the knowledge structure, research hotspots and trends of ZVI-based materials in this field. The results show that the research on ZVI-based materials in this field developed rapidly over the past 28 years. China is the greatest contributor with the most published articles and collaborations. Still, the USA has the most academic influence with the highest average citations per article. Chinese Academy of Sciences and Tongji University are the primary establishments that produced the greatest number of publications and had the highest h-index. Keyword cluster analysis indicates that the primary research topics are related to reductive dechlorination, sulfate radical, arsenic removal, graphene oxide, porous media, peroxymonosulfate, groundwater remediation, and permeable reactive barrier. Meanwhile, keyword burst analysis reveals that the primary research hotspots and frontiers of ZVI focus on its modification, the refractory and emerging contaminants treatment, persulfate activation, and electron transfer. However, no keywords or topics related to the environmental impact and toxicity of ZVI-based materials are available in the keyword clustering and burst analysis results, indicating this direction deserves more attention in future research. Through a comprehensive and in-depth bibliometric analysis, this paper provides new insight into the research hotspots and development trends of the research on ZVI-based materials in environmental remediation.

Visible light irradiation enhanced sulfidated zero-valent iron/peroxymonosulfate process for organic pollutant degradation.

This study developed a novel process named sulfidated zero-valent iron/peroxymonosulfate/visible light irradiation (S-mZVI/PMS/vis) for enhanced organic pollutant degradation. The S-mZVI/PMS/vis process exhibited remarkable catalytic activity, achieving a 99.6% rhodamine B (RhB) removal within 10 min. The degradation rate constant of RhB by the S-mZVI/PMS/vis process was found to be 6.49 and 79.84 times higher than that by the S-mZVI/PMS and PMS/vis processes, respectively. Furthermore, the S-mZVI/PMS/vis process worked efficiently across a wide pH range (3.0-9.0), and the result of five-cycle experiments demonstrated the excellent reusability and stability of S-mZVI. Radical quenching tests and electron paramagnetic resonance analysis indicated that ·O2-, 1O2, and h+ significantly contributed to the degradation of RhB through the S-mZVI/PMS/vis process. The visible light irradiation increased the Fe2+ concentration, improved the Fe3+/Fe2+ cycle, and consequently enhanced the PMS decomposition, reactive species production, and RhB degradation. This work offers a promising strategy to highly efficiently activate PMS for organic pollutants elimination from aqueous solutions.

Enhancement of hydrogenotrophic methanogenesis for methane production by nano zero-valent iron in soils.

Nanoscale zero-valent iron (nZVI) is attracting increasing attention as the most commonly used environmental remediation material. However, given the high surface area and strong reducing capabilities of nZVI, there is a lack of understanding regarding its effects on the complex anaerobic methane production process in flooded soils. To elucidate the mechanism of CH4 production in soil exposed to nZVI, paddy soil was collected and subjected to anaerobic culture under continuous flooding conditions, with various dosages of nZVI applied. The results showed that the introduction of nZVI into anaerobic flooded rice paddy systems promoted microbial utilization of acetate and carbon dioxide as carbon sources for methane production, ultimately leading to increased methane production. Following the introduction of nZVI into the soil, there was a rapid increase in hydrogen levels in the headspace, surpassing that of the control group. The hydrogen levels in both the experimental and control groups were depleted by the 29th day of culture. These findings suggest that nZVI exposure facilitates the enrichment of hydrogenotrophic methanogens, providing them with a favorable environment for growth. Additionally, it affected soil physicochemical properties by increasing pH and electrical conductivity. The metagenomic analysis further indicates that under exposure to nZVI, hydrogenotrophic methanogens, particularly Methanobacteriaceae and Methanocellaceae, were enriched. The relative abundance of genes such as mcrA and mcrB associated with methane production was increased. This study provides important theoretical insights into the response of key microbes, functional genes, and methane production pathways to nZVI during anaerobic methane production in rice paddy soils, offering fundamental insights into the long-term fate and risks associated with the introduction of nZVI into soils.

Peroxymonosulfate activation by walnut shell activated carbon supported nano zero-valent iron for the degradation of tetracycline: Performance, degradation pathway and mechanism.

In this study, activated carbon (WS-AC) was prepared from walnut shell. Nano-zero-valent iron (nZVI) was loaded on walnut shell activated carbon by liquid phase reduction method and used as catalyst (WS-AC/nZVI) to activate peroxymonosulfate (PMS) to efficiently degrade tetracycline (TC) in solution. The composite material with a mass ratio of WS-AC to nZVI of 1:1 has the highest catalytic performance for activating PMS to degrade TC. The results showed that under the conditions of TC concentration of 100 ppm, PMS dosage of 0.2 mM and WS-AC/nZVI dosage of 0.1 g/L, the removal efficiency of TC could reach 81%. Based on quenching experiments and electron spin resonance (EPR), it was verified that •OH, SO4•- and 1O2 bound on the catalyst surface were the main reactive oxygen species during the reaction. The intermediate products of TC were identified by liquid chromatography-mass spectrometry (HPLC-MS) and DFT calculation, and the possible degradation pathway of TC was proposed. The catalyst still maintained high removal efficiency of TC after four cycles of experiments, and the minimal iron loss on the surface of the catalyst indicated that it had good stability. The efficient and stable WS-AC/nZVI activated PMS showed great potential in the degradation of antibiotics.

Chemical and biological effects of zero-valent iron (ZVI) concentration on in-situ production of H2 from ZVI and bioconversion of CO2 into CH4 under anaerobic conditions.

The conversion of carbon dioxide (CO2) to methane (CH4) is a strategy for sequestering CO2. Zero-valent iron (ZVI) has been proposed as an alternative electron donor for the CO2 reduction to CH4. In this study, the effects of ZVI concentrations on the abiotic production of H2 (without the action of microorganisms) in the first part and on the biological conversion of CO2 to CH4 using ZVI as a direct electron donor in the second part were examined. In the abiotic H2 production, the increase in the ZVI concentration from 16 to 32, 64, and 96 g/L was found to have positive effects on both the amounts of H2 generated and the rates of H2 production because the extent of ZVI oxidation positively correlates with increasing surface area. Nevertheless, the increase in ZVI concentration from 96 to 224 g/L did not benefit the H2 production because the ZVI dissolution was suppressed by the increasing aqueous pH above 10. In the bioconversion of CO2 to CH4 using ZVI as an electron donor, the main methanogenesis pathway occurred via hydrogenotrophic methanogenesis at pH 8.7-9.5 driven by the genus Methanobacterium of the class Methanobacteria. At ZVI concentrations of 64 g/L and above, the production of volatile fatty acid (VFA) became clear. Acetate was the main VFA, indicating the induction of homoacetogenesis at ZVI concentrations of 64 g/L and above. In addition, the presence of propionate as the second major VFA suggests the production of propionate from CO2 and acetate under conditions with high H2 partial pressure. The results indicated that the pathway for ZVI/CO2 conversion to CH4 was competitive between hydrogenotrophic methanogenesis and homoacetogenesis.

Persulfate activation by nanoscale zero-valent iron supported by modified blast furnace slag for degradation of phenol wastewater.

Nano-zero valent iron (nZVI) was anchored and dispersed on the surface of acid-modified blast furnace slag (mBFS) through the liquid phase reduction method. The synthesized nZVI@mBFS composite exhibited remarkable ability to degrade phenol when used in conjunction with persulfate (PDS), 97.8% phenol could be eliminated in 30 min. All the anions like SO42-, HCO3-, H2PO4-, and CO32- were detrimental to the phenol degradation in nZVI@mBFS system. Moreover, electron paramagnetic resonance (EPR) analysis and radical scavenging tests confirmed that SO4•-, •OH and •O2- were the principal reactive oxygen species (ROSs) generated during the reaction process. The potential degradation pathways were also deduced based on the results obtained from gas chromatograph-mass spectrometer (GC-MS) analysis. Collectively, this study holds substantial significance in regards to recycling industrial solid wastes, devising efficient persulfate-activated materials, and treating wastewater.

Enhanced Cr(VI) removal and stabilization from bioleached wastewater by zero-valent iron coupled with hetero and autotrophic bacteria.

Zero-valent iron (Fe0) usually suffers from organic acid complexation and ferrochrome layer passivation in Cr(VI) removal from bioleached wastewater of Cr slag. In this work, a synergetic system combined Fe0 and mixed hetero/autotrophic bacteria was established to reduce and stabilize Cr(VI) from bioleached wastewater. Due to bacterial consumption of organic acid and hydrogen, severe iron corrosion and structured-Fe(II) mineral generation (e.g., magnetite and green rust) occurred on biotic Fe0 surface in terms of solid-phase characterization, which was crucial for Cr(VI) adsorption and reduction. Therefore, compared with the abiotic Fe0 system, this integrated system exhibited a 6.1-fold increase in Cr(VI) removal, with heterotrophic reduction contributing 3.4-fold and abiotic part promoted by hydrogen-autotrophic bacteria enhancing 2.7-fold. After reaction, the Cr valence distribution and X-ray photoelectron spectroscopy indicated that most Cr(VI) was converted into immobilized products such as FexCr1-x(OH)3, Cr2O3, and FeCr2O4 by biotic Fe0. Reoxidation experiment revealed that these products exhibited superior stability to the immobilized products generated by Fe0 or bacteria. Additionally, organic acid concentration and Fe0 dosage showed significantly positive correlation with Cr(VI) removal within the range of biological adaptation, which emphasized that heterotrophic and autotrophic bacteria acted essential roles in Cr(VI) removal. This work highlighted the enhanced effect of heterotrophic and autotrophic activities on Cr(VI) reduction and stabilization by Fe0 and offered a promising approach for bioleached wastewater treatment.

Achieving sustainable trichloroethylene removal from nitrate-containing groundwater: Effects of particle size and dosage of microscale zero-valent iron on its synergistic action with anaerobic bacteria.

The coupling of microscale zero-valent iron (mZVI) and anaerobic bacteria (AB) has gained increasing attention due to its ability to enhance dechlorination efficiency by combining the advantages of chemical and microbial reduction. However, the implementation of these coupling technologies at the field scale is challenging in terms of sustainability goals due to the coexistence of various natural electron acceptors in groundwater, which leads to limited electron selectivity and increased secondary risk. Therefore, this study used trichloroethylene (TCE) as a probe contaminant and nitrate (NO3-) as a typical co-occurring natural electron acceptor to optimize the overall sustainable remediation performance of an mZVI/AB coupled system by adjusting the mZVI particle size and dosage. Results revealed that mZVI particles of different sizes exhibit different microorganism activation capabilities. In contrast to its 2 µm and 7 µm counterparts, the 30 µm mZVI/AB system demonstrated a strong dosage-dependency in TCE removal and its product selectivity. Finally, multi-criteria analysis (MCA) methods were established to comprehensively rank the alternatives, and 30 µm mZVI (15 g/L dosage) was determined to be the best remediation strategy with the highest total sustainability score under all studied hydro-chemical conditions when equal weights were applied to technical, environmental, and economic indicators. Our work provides a paradigm for comprehensively assessing the sustainable remediation performance of chlorinated aliphatic hydrocarbons polluted groundwater in practical applications.

Effects of common dissolved anions on the efficiency of Fe0-based remediation systems.

Quiescent batch experiments were conducted to evaluate the influences of Cl-, F-, HCO3-, HPO42-, and SO42- on the reactivity of metallic iron (Fe0) for water remediation using the methylene blue (MB) method. Strong discoloration of MB indicates high availability of solid iron corrosion products (FeCPs). Tap water was used as an operational reference. Experiments were carried out in graduated test tubes (22 mL) for up to 45 d, using 0.1 g of Fe0 and 0.5 g of sand. Operational parameters investigated were (i) equilibration time (0-45 d), (ii) 4 different types of Fe0, (iii) anion concentration (10 values), and (iv) use of MB and Orange II (O-II). The degree of dye discoloration, the pH, and the iron concentration were monitored in each system. Relative to the reference system, HCO3- enhanced the extent of MB discoloration, while Cl-, F-, HPO42-, and SO42- inhibited it. A different behavior was observed for O-II discoloration: in particular, HCO3- inhibited O-II discoloration. The increased MB discoloration in the HCO3- system was justified by considering the availability of FeCPs as contaminant scavengers, pH increase, and contact time. The addition of any other anion initially delays the availability of FeCPs. Conflicting results in the literature can be attributed to the use of inappropriate experimental conditions. The results indicate that the application of Fe0-based systems for water remediation is a highly site-specific issue which has to include the anion chemistry of the water.

In-situ methane enrichment in anaerobic digestion of food waste slurry by nano zero-valent iron: Long-term performance and microbial community succession.

In this work, nano zero-valent iron (nZVI) was added to a lab-scale continuous stirring tank reactor (CSTR) for food waste slurry treatment, and the effect of dosing rate and dosage of nZVI were attempted to be changed. The results showed that anaerobic digestion (AD) efficiency and biomethanation stability were optimum under the daily dosing and dosage of 0.48 g/gTCOD. The average daily methane (CH4) yield reached 495.38 mL/gTCOD, which was 43.65% higher than that at control stage, and the maximum CH4 content reached 95%. However, under single dosing rate conditions, high nZVI concentrations caused microbial cell rupture and loosely bound extracellular polymeric substances (LB-EPS) precipitation degradation. The daily dosing rate promoted the hydrogenotrophic methanogenesis pathway, and the activity of coenzyme F420 increased by 400.29%. The microbial analysis indicated that daily addition of nZVI could promote the growth of acid-producing bacteria (Firmicutes and Bacteroidetes) and methanogens (Methanothrix).

Removal of Cu(II) by sodium hexametaphosphate and nano zero-valent iron modified calcium bentonite: characteristic, adsorption performance and mechanism.

Cu (II) is a toxic heavy metal commonly identified in groundwater contaminants. Bentonite-based cutoff wall is the most used method in isolating and adsorbing contaminants, while the bentonite in it easily to fail due to Cu(II) exchange. This study synthesized a novel material through the modification of calcium bentonite (CaB) utilizing sodium hexametaphosphate (SHMP) and nano zero-valent iron (NZVI). The characteristics, adsorption performance, and mechanism of the NZVI/SHMP-CaB were investigated comprehensively. The results showed that SHMP can disperse CaB and reduce flocculation, while NZVI can be further stabilized without agglomeration. The best adsorption performance of NZVI/SHMP-CaB could be obtained at the dosage of 2% SHMP and 4% NZVI. The NZVI/SHMP-CaB exhibited an outstanding removal efficiency of over 60% and 90% at a high Cu(II) concentration (pH = 6, Cu(II) = 300 mg/L) and acidic conditions (pH = 3-6, Cu(II) = 50 mg/L), respectively. The adsorption of Cu(II) by NZVI/SHMP-CaB followed a pseudo-second-order kinetic model, and fitting results from the Freundlich isothermal model suggested that the adsorption process occurred spontaneously. Besides the rapid surface adsorption on the NZVI/SHMP-CaB and ion exchange with interlayer ions in bentonite, the removal mechanism of Cu(II) also involved the chemical reduction to insoluble forms such as Cu0 and Cu2O. The generated FePO4 covered the surface of the homogenized NZVI particles, enhancing the resistance of NZVI/SHMP-CaB to acidic and oxidative environments. This study indicates that NZVI/SHMP-CaB is a promising alternative material which can be used for heavy metal removal from contaminated soil and water.

Evaluating the role of salinity in enhanced biogas production from two-stage anaerobic digestion of food waste by zero-valent iron.

Salts including NaCl are the most common food flavoring agents so they are often accumulated in food waste (FW) and have potential impact on anaerobic digestion (AD) of FW. In this study, the enhanced biogas production from two-stage anaerobic digestion (TSAD) of FW by microscale zero-valent iron (ZVI) under different salinity (3, 6, 9, and 15 g NaCl/L) was evaluated. Under salinity stress, ZVI becomes a continue-release electron donor due to the enhanced corrosion and dissolution effect and the slow-down surface passivation, further improving the performance of TSAD. Experimental results revealed that the biogas production including H2 and CH4 from TSAD with 10 g/L ZVI addition was promoted under salinity stress. The maximum H2 and CH4 yield (303.38 mL H2/g-VS and 253.84 mL CH4/g-VS) were observed at the salinity 9 g NaCl/L. Compared with that of zero salinity, they increased by 40.94% and 318.46%, respectively. Additionally, Sedimentibacter, an exoelectrogen that can participate in the direct interspecies electron transfer, also exhibited the highest relative abundance (34.96%) at the salinity 9 g NaCl/L. These findings obtained in this study might be of great importance for understanding the influence of salinity on the enhanced AD by ZVI.

New insights into long-lasting Cr(VI) removal from groundwater using in situ biosulfidated zero-valent iron with sulfate-reducing bacteria.

Sulfidation enhances the reactivity of zero-valent iron (ZVI) for Cr(VI) removal from groundwater. Current sulfidation methods mainly focus on chemical and mechanical sulfidation, and there has been little research on biosulfidation using sulfate-reducing bacteria (SRB) and its performance in Cr(VI) removal. Herein, the ability of the SRB-biosulfidated ZVI (SRB-ZVI) system was evaluated and compared with that of the Na2S-sulfidated ZVI system. The SRB-ZVI system forms a thicker and more porous FeSx layer than the Na2S-sulfidated ZVI system, resulting in more sufficient sulfidation of ZVI and a 2.5-times higher Cr(VI) removal rate than that of the Na2S-sulfidated ZVI system. The biosulfidated-ZVI granules and FeSx suspension are the major components of the SRB-ZVI system. The SRB-ZVI system exhibits a long-lasting (11 cycles) Cr(VI) removal performance owing to the regeneration of FeSx. However, the Na2S-sulfidated ZVI system can perform only two Cr(VI) removal cycles. SRB attached to biosulfidated-ZVI can survive in the presence of Cr(VI) because of the protection of the biogenic porous structure, whereas SRB in the suspension is inhibited. After Cr(VI) removal, SRB repopulates in the suspension from biosulfidated-ZVI and produce FeSx, thus providing conditions for subsequent Cr(VI) removal cycles. Overall, the synergistic effect of SRB and ZVI provides a more powerful and environmentally friendly sulfidation method, which has more advantageous for Cr(VI) removal than those of chemical sulfidation. This study provides a visionary in situ remediation strategy for groundwater contamination using ZVI-based technologies.

Defining quality assurance guidance for effective selection of technical grade zero-valent iron production batch for groundwater remediation using permeable reactive barrier.

Zero-valent iron (ZVI) applied to the remediation of contaminated groundwater (GW) in situ, especially using engineered permeable reactive barriers (PRBs), has been proven to be an effective reactive material. However, many of ZVI brands do not represent tailored reagents specifically regarding destroying pollutants in GW. Thus, their reactivity towards certain contaminants in GW may vary significantly in a wide range even with different production batches of the same ZVI brand. This issue has rarely been known and consequently not addressed to a higher extend so far. Therefore, this study implemented extensive, long-term column experiments followed by short-term batch experiments for chlorinated volatile organic compounds (cVOCs) degradation for developing a semi-empirical test methodology to thoroughly resolve this pivotal issue by achieving an improved quality assurance guidance regarding proper field-scale emplacement of different ZVI brands and their production batches. The results showed that during column experiments perchloroethylene (PCE) led to a significant degradation up to a certain period but sulfate-reducing microorganisms enhanced the dehalogenation and led approximately to 100 % PCE removal. However, the efficacy varied for different ZVI brands, i.e., Gotthart Maier (GM) and Sponge Iron (Responge®). Furthermore, it could be shown that it might even vary among different production batches of the same ZVI brand. It was also observed that evolution of sulfate-reducing microorganisms may improve the efficacy of PCE degradation vastly that occur at different intensities with different ZVI brands and their respective production batches over time. Further, comparing comprehensive long-term column (kobs = 0.0488 1/h) and short-term batch experiments (kobs = 0.07794 1/h) as well as refined kinetic analyses (kobs = 0.0424 1/h) clearly prove that an appropriate guidance protocol for successful full-scale in situ remediation is required for properly select the right ZVI brand and production batch before it is loaded to a PRB in the field.

Metagenomic analysis reveals the mechanisms of biochar supported nano zero-valent iron in two-phase anaerobic digestion of food waste: microbial community, CAZmey, functional genes and antibiotic resistance genes.

The mechanisms of biochar supported nano zero-valent iron (BC/nZVI) on two-phase anaerobic digestion of food waste were investigated. Results indicated that the performance of both acidogenic phase and methanogenic phase was effectively facilitated. BC/nZVI with the amount of 120 mg/L increased methane production by 32.21%. In addition, BC/nZVI facilitated direct interspecies electron transfer (DIET) between Geobacter and methanogens. Further analysis showed that BC/nZVI increased the abundance of most CAZymes in acidogenic phase. The study also found that BC/nZVI had positive effects on metabolic pathways and related functional genes. The abundances of acdA and ackA in acidogenic phase were increased by 151.75% and 36.26%, respectively, and the abundances of pilA and TorZ associated with DIET were also increased. Furthermore, BC/nZVI mainly removed IMP-12, CAU-1, cmeB, ErmR, MexW, ErmG, Bla2, vgaD, MuxA, and cpxA from this system, and reduced the antibiotic resistance genes for antibiotic inactivation resistance mechanisms.

Activity and recyclability enhancement of pH-dependent Fe0@BC-mediated heterogeneous sodium percarbonate (SPC)-reducing agents (RA) system.

Dyes pose great threats to the aquatic environment and human health. Fe0-based Fenton-like systems have been widely employed for the degradation of organic dyes. However, the regulation of degradability and recyclability was still unclear. In this study, Rhodamine B (RhB) was served as the model pollutant, hydroxylamine hydrochloride was selected as the RA, the natural photocatalysis system demonstrated stable operation. RA, as performance enhancement agent, was firstly reported in micro/nano-Zero-Valent Iron@Biochar (m/nZVI@BC) based SPC-RA system. Carrier size-fractionated m/nZVI@BC was fabricated by one-step carbothermal method. As a result, RA synergistically interacted with SPC, and the reaction time reduced from 15 min to 4 min. In the 0.010 g m/nZVI@BC-mediated SPC-RA system, over 95% of RhB (100 mg·L-1, 1041.667 mg·g-1) was successfully degraded. The maximum degradation ability could still exceed 1g·g-1 via 5 times repeated applications. Meanwhile, the loss of degradability, caused by halving SPC concentration could be compensated by RA dosage measurement. The entire degradation process was predominantly dominated by free radicals (•OH> 1O2> •O2-> •CO3-). Reactive oxidizing species (ROSs) were primarily excited by α-Fe0, Fe3C and N sites of biochar (BC). Light and BC carrier dedicated slight influence. These discoveries shed a light on the activity and recyclability regulation of catalytic material, aligning with the principles of green chemistry and cleaner production. This study demonstrates a novel approach to efficient management of solid waste disposal, reuse of waste biomass, advanced treatment of dye-containing wastewater, pollution control in aquatic environments.