Nano Zero-valent Iron Research Articles

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

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

Highly effective removal of 4-chloroaniline in water by nano zero-valent iron cooperated with microbial degradation

The misuse of aromatic amines like 4-chloroaniline (4-CA) has led to severe environmental and health issues. However, it’s difficult to be utilized by microorganisms for degradation. Nano-zero-valent iron (nZVI) is a promising material for the remediation of chloroaniline pollution, however, the synergistic effect and mechanism of nZVI with microorganisms for the degradation of 4-CA are still unclear. This study investigated the potential of 4-CA removal by the synergistic system involving nZVI and 4-CA degrading microbial flora. The results indicate that the addition of nZVI significantly enhanced the bio-degradation rate of 4-CA from 43.13 % to 62.26 %. Under conditions involving 0.1 % nZVI addition at a 24-hour interval, pH maintained at 7, and glucose as an external carbon source, the microbial biomass, antioxidant enzymes, and dehydrogenase were significantly increased, and the optimal 4-CA degradation rate achieved 68.79 %. Additionally, gas chromatography-mass spectrometry (GC-MS) analysis of intermediates indicated that the addition of nZVI reduced compounds containing benzene rings and enhanced the dechlorination efficiency. The microbial community remained stable during the 4-CA degradation process. This study illustrates the potential of nZVI in co-microbial remediation of 4-CA compounds in the environment.

Multifunctional schwertmannite-loaded nano zero-valent iron for highly efficient removal of hexavalent chrome from aqueous solution

Adsorption and reduction are important ways to remediate hexavalent chrome [Cr(VI)] which is extremely hazardous to human health. Previous studies have shown that schwertmannite (Sch) and nano zero-valent iron (nZVI) are potential materials with high adsorption and strong reduction for Cr(VI), respectively. However, it has been well known that bare nZVI has limitations in remediating Cr(VI) due to its susceptibility to self-aggregation and oxidation in practical applications. Hence to address the above limitations, nZVI was added into the internal pore structure of Sch (nZVI@Sch) in this study and Cr(VI) removal capacity by nZVI@Sch in aqueous solution were systematically investigated. Results showed that under the conditions that the concentration ratio of Fe2+ and Sch is 0.25 mol/L, Cr(VI) initial concentration of 10 mmol/L, initial pH of 3, Cr(VI) remediation ability of nZVI@Sch reached up to 114.03 mg/g (with freeze-drying) and 165.69 mg/g (without freeze-drying) in 4 hours, respectively. Based on the characterization analysis of SEM-EDS, XPS and Zeta potential, the multifunctional synergistic effects of capture-reduction-adsorption-coprecipitation as a mechanism for the removal of Cr(VI) by nZVI@Sch were proposed in this study. This study provided a new remediation material and suggestions for chromium pollution remediation.

In situ carbothermal synthesis of carbonized bacterial cellulose embedded with nano zero-valent iron for removal of Cr(VI)

Carbonized bacterial cellulose embedded with highly dispersed nano zero-valent iron (nZVI), denoted as nZVI@CBC, was prepared through one-step in situ carbothermal treatment of bacterial cellulose adsorbing iron(III) nitrate. The structure characteristics of nZVI@CBC and its performance in removing hexavalent chromium Cr(VI) were investigated. Results showed the formation of nZVI@CBC with a surface area of 409.61 m2/g at 800 °C, with nZVI particles of mean size 28.2 nm well distributed within the fibrous network of CBC. The stability of nZVI was enhanced by its carbon coating, despite some inevitable oxidation of exposed nZVI. Batch experiments demonstrated that nZVI@CBC exhibited superior removal efficiency compared to bare nZVI and CBC. Under optimal conditions, nZVI@CBC exhibited a high Cr(VI) adsorption capacity of up to 372.42 mg/g. Therefore, nZVI@CBC shows promise as an effective adsorbent for remediating Cr(VI) pollution in water.

Optimized combination of zero-valent iron and oxygen-releasing biochar as cathodes of microbial fuel cells to enhance copper migration in sediment

Membrane-less single-medium sediment microbial fuel cells (single-SMFC) can remove Cu2+ from sediment through electromigration. However, the high mass transfer resistance of the sediment and amount of oxygen at the cathode of the SMFC limit its Cu2+ removal ability. Therefore, this study used an oxygen-releasing bead (ORB) for slow oxygen release to increase oxygen at the SMFC cathode and improve the mass transfer property of the sediment. Resultantly, the copper removal efficiency of SMFC increased significantly. Response surface methodology was used to optimize the nano zero-valent iron (nZVI)-modified biochar as the catalyst to enhance the ability of the modified ORB (ORBm) to remove Cu2+ and slow release of O2. The maximum Cu2+ removal (95 %) and the slowest O2 release rate (0.41 mg O2/d·g ORBm) were obtained when the CaO2 content and ratio of nZVI-modified biochar to unmodified biochar were 0.99 g and 4.95, respectively. When the optimized ORBm was placed at the single-SMFC cathode, the voltage output and copper removal increased by 4.6 and 2.1 times, respectively, compared with the system without ORBm. This shows that the ORBm can improve the migration of Cu2+ in the sediment, providing a promising remediation method for Cu-contaminated sediments.

Nano Zero-Valent Iron (nZVI) Encapsulated with ABS (nZVI/(ABS + EC)) for Sustainable Denitrification Performance and Anti-Aggregation

Aggregation and sharp reactivity decrease are the key problems of using nano zero-valent iron (nZVI) as a potential reaction medium for a permeable reactive barrier (PRB). In this study, nZVI particles encapsulated within an acrylonitrile–butadiene–styrene (ABS) matrix (nZVI/(ABS + EC)) was fabricated, which for the first time successfully simultaneously solved the above problems via accurately regulating the distribution of nZVI particles in the ABS matrix and regulating the contact between nZVI particles and the contaminated aqueous environment. In addition, the size and number of the pores throughout the ABS matrix were first regulated by ethyl cellulose (EC) for the purpose of controlling the contact between nZVI particles and the nitrate contaminant, affording apparent rate constants (kobs) for denitrification performance in the range of 0.0423 to 0.0820 min−1. The remediation of simulated nitrate-contaminated solution by nZVI/(ABS + EC) was suitably described by the first-order kinetics model, with kobs ranging from 0.0423 to 0.2036 min−1, and functional relationship models of kobs with the dosages of EC (dEC) and nZVI (dFe) during encapsulation were developed for the quantitative regulation of a sustainable denitrification performance. Results revealed that encapsulation prevents the aggregation of nZVI, rendering a sustainable denitrification performance of the material; the denitrification performance was demonstrated to be affected and quantitatively regulated by the encapsulation and application conditions. Using nZVI/(ABS + EC) as the reaction medium for PRB, the pore blocking of PRB can be avoided, and the sustainable remediation performance can be quantitatively regulated and predicted.

Combined exposure to decabromodiphenyl ether and nano zero-valent iron aggravated oxidative stress and interfered with metabolism in earthworms

Decabromodiphenyl ether (BDE-209) is a common brominated flame retardant in electronic waste, and nano zero-valent iron (nZVI) is a new material in the field of environmental remediation. Little is known about how BDE-209 and nZVI combined exposure influences soil organisms. During the 28 days study, we determined the effects of single and combined exposures to BDE-209 and nZVI on the oxidative stress and metabolic response of earthworms (Eisenia fetida). On day 7, compared to CK, malondialdehyde (MDA) content increased in most combined exposure groups. To remove MDA and reactive oxygen species (ROS), superoxide dismutase (SOD), catalase (CAT), and peroxidase (POD) activities were induced in most combined exposure groups. On day 28, compared to CK, the activities of SOD and CAT were inhibited, while POD activity was significantly induced, indicating that POD plays an important role in scavenging ROS. Combined exposure to BDE-209 and nZVI significantly affected amino acid biosynthesis and metabolism, purine metabolism, and aminoacyl-tRNA biosynthesis pathways, interfered with energy metabolism, and aggravated oxidative stress in earthworms. These findings provide a basis for assessing the ecological impacts of using nZVI to remediate soils contaminated with BDE-209 from electronic waste.

From Nano Zero-Valent Iron to Nanocomposite Materials for Sustainable Water Treatment

Nano zero-valent iron (nZVI) is a well-known and effective remediation agent for various water contaminants. However, the challenges associated with its application, such as agglomeration and difficulty in recovery, have limited its effectiveness in large-scale treatment processes. In recent years, the development of nZVI nanocomposites has shown promise in addressing these challenges, as they offer improved stability, reactivity, and recoverability. This paper reviews the latest advancements in nZVI nanocomposites for water treatment and discusses their potential for the sustainable remediation of various contaminants, including heavy metals, organic contaminants, and emerging contaminants. The potential applications, limitations, and future prospects of nZVI nanocomposites in water treatment are discussed in detail. Overall, the findings suggest that nZVI nanocomposites have significant potential for sustainable water treatment and can contribute to the development of cost-effective and environmentally friendly water treatment solutions.

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).

Metabolomic and gut-microbial responses of earthworms exposed to microcystins and nano zero-valent iron in soil

The earthworm-based vermiremediation facilitated with benign chemicals such as nano zero-valent iron (nZVI) is a promising approach for the remediation of a variety of soil contaminants including cyanotoxins. As the most toxic cyanotoxin, microcystin-LR (MC-LR) enter soil via runoff, irrigated surface water and sewage, and the application of cyanobacterial biofertilizers as part of the sustainable agricultural practice. Earthworms in such remediation systems must sustain the potential risk from both nZVI and MC-LR. In the present study, earthworms (Eisenia fetida) were exposed up to 14 days to MC-LR and nZVI (individually and in mixture), and the toxicity was investigated at both the organismal and metabolic levels, including growth, tissue damage, oxidative stress, metabolic response and gut microbiota. Results showed that co-exposure of MC-LR and nZVI is less potent to earthworms than that of separate exposure. Histological observations in the co-exposure group revealed only minor epidermal brokenness, and KEGG enrichment analysis showed that co-exposure induced earthworms to regulate glutathione biosynthesis for detoxification and reduced adverse effects from MC-LR. The combined use of nZVI promoted the growth and reproduction of soil and earthworm gut bacteria (e.g., Sphingobacterium and Acinetobacter) responsible for the degradation of MC-LR, which might explain the observed antagonism between nZVI and MC-LR in earthworm microcosm. Our study suggests the beneficial use of nZVI to detoxify pollutants in earthworm-based vermiremediation systems where freshwater containing cyanobacterial blooms is frequently used to irrigate soil and supply water for the growth and metabolism of earthworms.

Mechanistic insights into manganese oxide impacting the oxidation and transport of Cr(III) immobilized by nano-zero valent charged ion particles in water-saturated porous media

The presence of manganese oxide (MnO2) could influence the stability of green-synthesized nano-zero valent iron (nZVI@GT) associated with trivalent chromium (Cr(III)) after its excess application in the in situ remediation of hexachromium (Cr(VI)) contaminated soil. The research findings revealed that the co-transport of the remaining nZVI@GT with Cr(III) was substantially inhibited by high δ-MnO2 concentrations due to the formation of hetero-aggregates between nZVI@GT and δ-MnO2, resulting in an increased irreversible attachment parameter at second-site in a two-site kinetic attachment model. Simultaneously, the Cr(III) complex immobilized on nZVI@GT could be oxidized leading to high levels of Cr(VI) leaching at high δ-MnO2 concentrations. During this process, Mn(IV) was converted to Mn(III)/Mn(II). Subsequently, leachate containing a partial amount of Cr(VI) preferentially adsorbed onto the nZVI@GT surface, enhancing the dispersion of the nZVI@GT and δ-MnO2 agglomerates. Thereafter, nZVI@GT transportability was enhanced with a decreased second-site attachment parameter and the flow content of dissolved Cr(VI) was increased to double, also increasing the potential risk of Cr(VI) being carried by nZVI@GT to underground water systems. This study provides theoretical support for preserving the long-term stability of nZVI@GT after the in situ remediation of heavy metal-contaminated sites in the presence of δ-MnO2.

Exploring the synergistic effect of chromium (Cr) tolerant Pseudomonas aeruginosa and nano zero valent iron (nZVI) for suppressing Cr uptake in Aloe Vera

Chromium (Cr) contamination of soil has substantially deteriorated soil health and has interfered with sustainable agricultural production worldwide and therefore, its remediation is inevitable. Inoculation of plant growth promoting rhizobacteria (PGPR) in association with nanotechnology has exerted broad based impacts in agriculture, and there is an urgent need to exploit their synergism in contaminated soils. Here, we investigated the effect of co-application of Cr-tolerant “Pseudomonas aeruginosa CKQ9” strain and nano zerovalent iron (nZVI) in improving the phytoremediation potential of aloe vera (Aloe barbadensis L.) under Cr contamination. Soil was contaminated by using potassium dichromate (K2Cr2O7) salt and 15 mg kg−1 contamination level in soil was maintained via spiking and exposure to Cr lasted throughout the duration of the experiment (120 days). We observed that the co-application alleviated the adverse impacts of Cr on aloe vera, and improved various plant attributes such as plant height, root area, number of leaves and gel contents by 51, 137, 67 and 49% respectively as compared to control treatment under Cr contamination. Similarly, significant boost in the activities of various antioxidants including catalase (124%), superoxide dismutase (87%), ascorbate peroxidase (36%), peroxidase (89%) and proline (34%) was pragmatic under contaminated soil conditions. In terms of soil Cr concentration and its plant uptake, co-application of P. aeruginosa and nZVI also reduced available Cr concentration in soil (50%), roots (77%) and leaves (84%), while simultaneously increasing the relative production index by 225% than un-inoculated control. Hence, integrating PGPR with nZVI can be an effective strategy for enhancing the phytoremediation potential of aloe vera.

Research Progress on the Degradation of Organic Pollutants in Water by Activated Persulfate Using Biochar-Loaded Nano Zero-Valent Iron.

Biochar (BC) is a new type of carbon material with a high specific surface area, porous structure, and good adsorption capacity, which can effectively adsorb and enrich organic pollutants. Meanwhile, nano zero-valent iron (nZVI) has excellent catalytic activity and can rapidly degrade organic pollutants through reduction and oxidation reactions. The combined utilization of BC and nZVI can not only give full play to their advantages in the adsorption and catalytic degradation of organic pollutants, but also help to reduce the agglomeration of nZVI, thus improving its efficiency in water treatment and providing strong technical support for water resources protection and environmental quality improvement. This article provides a detailed introduction to the preparation method and characterization technology, reaction mechanism, influencing factors, and specific applications of BC and nZVI, and elaborates on the research progress of BC-nZVI in activating persulfate (PS) to degrade organic pollutants in water. It has been proven experimentally that BC-nZVI can effectively remove phenols, dyes, pesticides, and other organic pollutants. Meanwhile, in response to the existing problems in current research, this article proposes future research directions and challenges, and summarizes the application prospects and development trends of BC-nZVI in water treatment. In summary, BC-nZVI-activated PS is an efficient technology for degrading organic pollutants in water, providing an effective solution for protecting water resources and improving environmental quality, and has significant application value.

Nano zero-valent iron and melatonin synergistically alters uptake and translocation of Cd and As in soil-rice system and mechanism in soil chemistry and microbiology

Nanoscale zero-valent iron (Fe) is a promising nanomaterial for remediating heavy metal-contaminated soils. Melatonin (MT) is essential to alleviate environmental stress in plants. However, the conjunction effects of Fe and MT (FeMT) on rice Cd, As accumulation and the mechanism of soil chemical and microbial factors interaction are unclear. Here, a pot experiment was conducted to evaluated the effects of the FeMT for rice Cd, As accumulation and underlying mechanisms. The findings showed that FeMT significantly reduced grains Cd by 92%–87% and As by over 90%, whereas improving grains Fe by over 213%. Soil available-Cd and iron plaques-Cd (extracted by dithionite-citrate-bicarbonate solution, DCB-Cd) significantly regulated roots Cd, thus affected Cd transport to grains. Soil pH significantly affected soil As and DCB-As, which further influenced roots As uptake and the transport to shoots and grains. The interactions between the soil bacterial community and soil Fe, available Fe, and DCB-Fe together affected root Fe absorption and transportation in rice. FeMT significantly influenced rhizosphere soil bacterial α- and β-diversity. Firmicutes as the dominant phylum exhibited a significant positive response to FeMT measure, and acted a key role in reducing soil Cd and As availability mainly by improving iron-manganese plaques. The increase of soil pH caused by FeMT was beneficial only for Actinobacteriota growth, which reduced Cd, As availability probably through complexation and adsorption. FeMT also showed greater potential in reducing human health and ecological risks by rice consumption and straw returning. These results showed the important role of both soil chemical and microbial factors in FeMT-mediated rice Cd, As reduction efficiency. This study opens a novel strategy for safe rice production and improvement of rice iron nutrition level in heavy-metals polluted soil, but also provides new insights into the intricate regulatory relationships among soil biochemistry, toxic elements, microorganism, and plants.

Coupling and electronic synergistic effects of Fe/CeO2 composite to achieve high efficiency and selectivity for RWGS reaction

Transition metal iron, because of its high oxygen mobility, excellent thermal stability and low price, is often used in the study of RWGS reaction. However, the bottleneck problem of iron-based catalysts is the poor CO2 conversion rate. Herein, the Fe/CeO2 composite catalyst with Fe-O-Ce was successfully constructed, which has both high CO2 conversion and high CO selectivity for the low-temperature RWGS reaction. Furthermore, the influence of Fe0 contents is studied, and the result indicated that the CO2 conversion rate and CO selectivity are up to 50.05% and 100% at 500 ºC by the use of 20Fe/CeO2. Moreover, CeO2 is the best catalyst holder than the others. The physical and chemical properties of the catalysts are investigated by in-situ XPS, XRD, low-temperature N2 absorption-desorption (BET) and CO2-TPD. Nano zero-valent iron (Fe0) is the main active center for the RWGS reaction, which easily releases the outer electrons to activate reactant molecules. The introduction of the CeO2 is conducive to the high dispersion of Fe0 nanoparticles and the formation of abundant active centers. With the increase of Fe loading, the electron-rich Fe0 induces a strong electronic effect on the electron-deficient CeO2. The regularity of catalyst are changed by a large amount of zero-valent iron entering into the CeO2 lattice, then formed a lot of Fe-O-Ce solid solution. A large amount of zero-valent iron enter into the CeO2 lattice, inhibiting the grain growth and aggregation of monometallic species, and promoting nano Fe species highly dispersed on CeO2 carriers, leading more active centers exposure. Meanwhile, the abundant oxygen vacancy on xFe/CeO2 surface is advantage for the adsorption and activation of H2 and CO2 molecules. Therefore, the coupling and electronic synergistic effects of the active component Fe0 and the carrier CeO2 make xFe/CeO2 becoming a promising candidate catalyst for RWGS reaction.

Surfactant enhanced persulfate system for the synergistic oxidation and reduction of mixed chlorinated hydrocarbons

Surfactant-enhanced in-situ chemical oxidation (S-ISCO) is widely applied in soil and groundwater remediation. However, the role of surfactants in the reactive species (RSs) transformation remains inadequately explored. This work introduced nonionic surfactant Tween-80 (TW-80) into a nano zero-valent iron (nZVI) activated persulfate (PS) system. The findings indicate that PS/nZVI/TW-80 system can realize the concurrent removal of trichloroethylene (TCE), tetrachloroethene (PCE), and carbon tetrachloride (CT), whereas CT cannot be eliminated without TW-80 presence. Further analysis unveiled that hydroxyl (HO•) and sulfate radicals (SO4－•) were the primary species for TCE and PCE degradation, while CT was reductively eliminated by surfactant radicals generated from TW-80. Moreover, the surfactant radicals were found to accelerate Fe(III)/Fe(II) cycle, reduce the production of iron sludge, and increase PS decomposition. The possible degradation routes of mixed chlorinated hydrocarbons (CHCs) and the decomposition pathways of TW-80 were proposed through the density function theory (DFT) calculation and intermediates analysis. Additionally, the effects of other nonionic surfactants on the simultaneous removal of TCE, PCE, and CT, and the practical applications using the actual contaminated groundwater were also evaluated. This study provides theoretical support for the simultaneous removal of CHCs, particularly those containing perchlorinated contaminants, using the S-ISCO techniques.

Carbon nanotubes mediate electron transfer between Shewanella oneidenis MR-1 and nano zero-valent iron to enhance the elimination of Cr(VI) from aqueous media

Nano zero-valent iron (nZVI) has been widely employed for the elimination of heavy metals from wastewater. However, the practical application of nZVI is greatly limited due to its fast aggregation and surface passivation. In this study, a carbon nanotube-supported nZVI composite (nZVI@CNTs) was synthesized and coupled with Shewanella oneidensis MR-1 to enhance the removal of Cr(VI) from aqueous media. The results demonstrated that the coupling of nZVI@CNTs and MR-1 (nZVI@CNTs/MR-1) exhibited superior performance in eliminating Cr(VI) compared to using nZVI@CNTs or MR-1 alone. Electrochemical characterization demonstrated that CNTs acting as electron shuttles improve the electron transfer from MR-1 to nZVI, thus facilitating the passivation layer dissolution. XRD analysis proved that MR-1 can effectively promote the dissolution of the Fe(III) passivation layer with the existence of CNTs. FTIR and XPS analyses confirmed that CNTs contain many functional groups (such as C − C and C = O) related to extracellular electron transfer, thus promoting the electron transfer of MR-1 to nZVI. Three-dimensional excitation-emission matrix (3D-EEM) analysis showed that the extracellular polymeric substances (EPS) generated from MR-1 participated in the Cr(VI) elimination. The mechanism analysis demonstrated the Fe(II) dissolved from the nZVI passivation layer reduces Cr(VI) to Cr(III) and then removes it by co-precipitation, and the EPS secreted by MR-1 also participates in the Cr(VI) adsorption and reduction. Generally, the coupling of nZVI@CNTs and MR-1 successfully addresses the drawbacks of nZVI and demonstrates a remarkable ability to remove Cr(VI).

Conductive materials and applied potential to augment methanogenesis for biogas upgradation: Acidogenic synergy, CO2 dynamics and sustainability analysis

Methane (CH4) and carbon dioxide (CO2) make up the majority of the raw biogas produced by anaerobic digestion (AD). Increasing the process intensity by concurrently consuming CO2 in the presence of electron donors will enhance the gross calorific value of the biogas. The use of conductive materials (CM) and an electro-methanogenic (EM) process was evaluated to study carbon conversion efficiency to CH4 with simultaneous biogas upgradation. Five reactors (R1-control; R2-Granular Activated Carbon (GAC); R3- Nano Zero Valent Iron (NZVI); R4- Closed Circuit (CC); R5-Applied Potential (AP)) were operated using glucose as a source of carbon (30 g/L) to relatively examine the sustainable effect of CM and EM on methanogenesis. Higher biogas yield with higher CH4 production and accumulation of acetic acid was observed more in the NZVI system followed by AP, CC, GAC, and Control operation. NZVI supplemented significantly added to biogas upgradation (7.6 L) with a concurrent CO2 decrease (87%) as compared to the GAC (3.868 L, 43%) and EM (AP, 4.89 L, 52%; CC, 4.73 L, 49%) but its sacrificial and oxidation nature offsets its translation potential. The electron flux generated in AP and CC reactors had a strong regulatory effect that increased CO2 conversion and utilization towards CH4 compared to other circumstances. The genus-level metagenomic analysis showed a predominance of Clostridium, Ruminococcus, and Acetobacter species in all the reactors except the control. The life cycle assessment (LCA) analysis depicted that the system variation studied showed relatively low CO2 emission in the test condition with NZVI showing the least emission followed by AP and CC. This work offers a method for improving overall CH4 production while overcoming the constraints in methanogenesis, using the influence of in situ carbon flux making the process sustainable.

Oxalate modification enabled advanced phosphate removal of nZVI: In Situ formed surface ternary complex and altered multi-stage adsorption process

Nano zero-valent iron (nZVI) is a promising phosphate adsorbent for advanced phosphate removal. However, the rapid passivation of nZVI and the low activity of adsorption sites seriously limit its phosphate removal performance, accounting for its inapplicability to meet the emission criteria of 0.1 mg P/L phosphate. In this study, we report that the oxalate modification can inhibit the passivation of nZVI and alter the multi-stage phosphate adsorption mechanism by changing the adsorption sites. As expected, the stronger anti-passivation ability of oxalate modified nZVI (OX-nZVI) strongly favored its phosphate adsorption. Interestingly, the oxalate modification endowed the surface Fe(III) sites with the lowest chemisorption energy and the fastest phosphate adsorption ability than the other adsorption sites, by in situ forming a Fe(III)-phosphate-oxalate ternary complex, therefore enabling an advanced phosphate removal process. At an initial phosphate concentration of 1.00 mg P/L, pH of 6.0 and a dosage of 0.3 g/L of adsorbents, OX-nZVI exhibited faster phosphate removal rate (0.11 g/mg/min) and lower residual phosphate level (0.02 mg P/L) than nZVI (0.055 g/mg/min and 0.19 mg P/L). This study sheds light on the importance of site manipulation in the development of high-performance adsorbents, and offers a facile surface modification strategy to prepare superior iron-based materials for advanced phosphate removal.

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

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