Zero-valent Iron Research Articles

Revealing the catalytic behavior of different types ZVI (powder Fe0, sponge Fe1, foam Fe2) in US/Fex/PDS and its effect on the dewaterability of waste activated sludge

The ultrasound (US) irradiation-coupled zero-valent iron (ZVI) activated persulfate system could improve dewatering performance, reduce WAS volume, decrease transport and final disposal costs. However, there are huge differences between various types of ZVI on activation efficiency, reaction mechanism, and application potential in WAS conditioning process. In this study, three ZVI (Fex) catalysts (Fe0 powder iron, Fe1 sponge iron and Fe2 foam iron) were used in the US/PDS system, whose catalytic performance and the fundamentals of the WAS conditioning were explored and compared. The results showed that the capillary suction time (CST) reduction rates were 89 %, 85 %, and 87 % in US/Fe0/PDS, US/Fe1/PDS, and US/Fe2/PDS, respectively, which indicated that the US/Fex/PDS system had an outstanding conditioning performance. The WAS reduction rate was US/Fe1/PDS > US/Fe2/PDS > US/Fe0/PDS attributed to Fe1 surface activate sites. Similarly, the organic matters characterization showed soluble protein content (PN), polysaccharide content (PS), and microbial by-products were significantly reduced in the US/Fe1/PDS system. Further examination of the thermodynamic parameters revealed that the WAS cohesive interfacial energy (ΔGslscoh) was minimally reduced to promote release of bound water in the system due to the effective regulation of intermolecular forces. In addition, examination of the trivalent iron/divalent iron ratio (Fe3+/Fe2+) to assess the efficacy of ferric ion recycling showed a significant advantage for US/Fe1/PDS system. On the basis of improving catalyst utilization, PDS produced SO4·- that dominated free radicals to condition WAS, improve dewaterability and achieve WAS reduction. Finally, evaluating laboratory WAS conditioning results and costs, US/Fe1/PDS system has potential applications value.

Unveiling trends in migration of iron-based nanoparticles in saturated porous media

Nanoscale zero-valent iron (nZVI) particles are routinely used for environmental remediation, but their transport dynamics in different settings remain unclear, hindering optimization. This study introduces a novel approach to predicting nZVI transport in saturated porous model environment. The method employs advanced long column devices for real-time monitoring via controlled magnetic susceptibility measurements. Numerical modeling with a modified version of the MNMs 2023 software was then used to predict nZVI and its derivatives mobility in field-like conditions, offering insights into the radius of influence (ROI) and shape factor (SF) of their distribution. A standard nZVI precursor was compared with its four major commercial derivatives: nitrided, polyacrylic acid-coated, oxide-passivated, and sulfidated nZVI. All these iron-based nanoparticles exhibited identical particle sizes, morphologies, surface areas, and phase compositions, isolating surface properties, dominated by charge, as the sole variable affecting their mobility. The study revealed optimal transport when the surface charge of nZVI and its derivatives was strongly negative, while rapid aggregation of nZVI derivatives due magnetic attraction reduced their mobility. Modeling predictions based on column scale-up, indicated that detectable concentrations of 20 g L⁻1 were found at distances ranging from 0.4 to 1.1 m from the injection well. Slightly sulfidated nZVI traveled farther than the nZVI precursor and ensured more homogenous particle distribution around the well. Organically modified nZVI migrated the longest distances but showed particle accumulation close to the injection point. The findings suggest that minimal sulfidation combined with organic modification of nZVI surfaces may effectively enhance radial and vertical nZVI distribution in aquifers. Such improvements increase the commercial viability of modified nZVI, reduce their adverse impacts, and boosts their practical applications in real-world scenarios.

Sustainable Abiotic-Biotic Dechlorination of Perchloroethene with Sulfidated Nanoscale Zero-Valent Iron as Electron Donor Source.

Combining organohalide-respiring bacteria with nanoscale zero-valent iron (nZVI) represents a promising approach for remediating chloroethene-contaminated aquifers. However, limited information is available regarding their synergistic dechlorinating ability for chloroethenes when nZVI is sulfidated (S-nZVI) under the organic electron donor-limited conditions typically found in deep aquifers. Herein, we developed a combined system utilizing a mixed culture containing Dehalococcoides (Dhc) and S-nZVI particles, which achieved sustainable dechlorination with repeated rounds of spiking with 110 μM perchloroethene (PCE). The relative abundance of Dhc considerably increased from 5.2 to 91.5% after five rounds of spiking with PCE, as evidenced by 16S rRNA gene amplicon sequencing. S-nZVI corrosion generated hydrogen as an electron donor for Dhc and other volatile fatty acid (VFA)-producing bacteria. Electron balance analysis indicated that 68.1% of electrons from Fe0 consumed in S-nZVI were involved in dechlorination, and 6.2, 1.1, and 3.2% were stored in formate, acetate, and other VFAs, respectively. The produced acetate possibly served as a carbon source for Dhc. Metagenomic analysis revealed that Desulfovibrio, Syntrophomonas, Clostridium, and Mesotoga were likely involved in VFA production. These findings provide valuable insights into the synergistic mechanisms of biotic and abiotic dechlorination, with important implications for sustainable remediation of electron donor-limited aquifers contaminated by chloroethenes.

Research progress of nanoscale zero-valent iron in synergistic combinations of denitrifying bacteria for nitrate removal

Nitrate (NO3--N) is a common inorganic nitrogen pollutant in water. Excessive NO3--N can lead to water eutrophication and threaten human health. Nanoscale zero-valent iron (nZVI) has attracted much attention in NO3--N removal due to its high specific surface and excellent electron donor properties. The combination of nZVI and denitrifying bacteria (DNB) demonstrates high efficiency in converting NO3--N into N2. This approach not only substantially enhances the removal rate of NO3--N but also exhibits superior environmental sustainability compared with conventional chemical denitrification methods. Accordingly, it holds substantial promise for mitigating NO3--N pollution and warrants further exploration in the pollution control. Therefore, it is necessary to understand the interaction mechanism between nZVI and DNB for NO3--N removal. This paper details the factors affecting the removal of NO3--N by nZVI combined with DNB, reviews the latest research progress in this field, elaborates on the interaction mechanism between nZVI and DNB for NO3--N removal, and discusses the challenges and future research directions of NO3--N removal by nZVI combined with DNB. This review aims to provide a theoretical basis for the development of efficient approaches for the remediation of NO3--N pollution.

Removal of Cr(VI) in groundwater by controlled release materials based on nano zero-valent iron and activated carbon

ABSTRACT The use of nano zero-valent iron (nZVI) materials for groundwater Cr(VI) removal encountered challenges of agglomeration and low removal efficiency. Controlled release materials (CRMs) gradually release reactive substances or reducing agents, prolonging the release time. Here, we report the development of novel CRMs containing nZVI and activated carbon (AC). During the removal of Cr(VI) in groundwater, the prepared AC/nZVI/CRMs slowly released nZVI, greatly reducing the agglomeration of nZVI. The adsorption capacity of AC-containing CRMs prolonged the residence time of Cr(VI) in water, improving the removal efficiency of the AC/nZVI/CRMs. We found that lower pH enhanced the removal of Cr(VI) by the AC/nZVI/CRMs from simulated groundwater. The removal efficiency of the AC/nZVI/CRMs was also affected by the simulated groundwater environment and decreased with the increasing flow rate of the groundwater. Our results suggested that these novel nZVI-containing CRMs minimized agglomeration during the removal of Cr(VI) by nZVI, exhibited enhanced efficiency under acidic conditions, and facilitated Cr(VI) removal from similar groundwater environments.

Long-term performance and mechanism of in-situ biogenetic sulfidated zero-valent iron for enhanced nitrate reduction

The biogenetic sulfidation of zero-valent iron (BS-ZVI) by sulfate-reducing bacteria (SRB) has been demonstrated to enhance the reactivity of ZVI. However, long-term performance of BS-ZVI and related mechanism were still unknown. Therefore, columns containing sponge iron and SRB are built to prepare BS-ZVI in-situ and study its long-term performance. Over 80 % of NO3‾ was reduced to NH4+ by in-situ BS-ZVI within 140 days, which was higher than the sole ZVI treatment (40 %-60 %). The bonding of ZVI and FeSx was in-situ firstly and finally loaded on ZVI. The reduction of Fe(III) by S(−II) and SRB contributed to the formation of FeSx, which improved the electrons transfer. Moreover, BS-ZVI enhanced the enzymes activity of SRB, thus accelerating the metabolic transformation of lactic acid to acetic acid. The accumulation of acetic acid enhanced the removal efficiency of NO3‾ through the dissolution of passivation layer. Overall, this study demonstrated a reactivity enhancement of ZVI through biogenetic sulfidation, which provided a new alternative method for the remediation of groundwater.

Significant improvement in the removal performance of decimeter-sized zero-valent iron plates for mixed heavy metal ions in wastewater by enhancing surface sharpness

This study aims to lower the work function (Wa) of a decimeter-sized zero-valent iron plate (DZVIP) by introducing surface sharpness (TDZVIP) during stirring. Sharpness was achieved by cutting isosceles triangles with heights of 1 cm and varying apex angles (α) of 10˚, 20˚, 30˚, 40˚, and 50˚. A mixed simulated wastewater containing Cu(II), Te(IV), Se(IV), As(III), Bi(III), and Pb(II) at concentrations exceeding emission standards was prepared. Results indicate that the removal process exhibits mixed kinetic behavior, and sharpness significantly enhances the removal capacity (Re), mean removal rate (Vm), recycling performance, and final discharge quality. The Vm values for Cu(II), Te(IV), Se(IV), As(III), Bi(III), and Pb(II) over TDZVIP with optimized α are 2.34, 1.97, 1.51, 1.59, 4.09, and 1.53 times higher, respectively, than those over PDZVIP (without sharpness). UPS measurements provide direct evidence of Wa reduction, while XRD offers indirect confirmation. This is the first time the Wa of the amorphous shell has been identified and verified as a critical potential barrier for core electrons transferring from the DZVIP surface to wastewater. Additionally, it has been successfully reduced by incorporating surface sharpness and stirring, leading to enhanced removal efficiency, improved recycling performance, and higher final discharge quality.

Selective Tl(I) Removal by Prussian Blue–Zero Valent Iron Nanoparticles

Selective Tl(I) Removal by Prussian Blue–Zero Valent Iron Nanoparticles

Enhanced Treatment of Antimony Mine Wastewater by Sulfidated Micro Zerovalent Iron (S-mZVI).

Commercial micron zerovalent iron (mZVI) and sulfur were used to prepare sulfidated micro zerovalent iron (S-mZVI) through ball milling. The corrosion potentials of mZVI and S-mZVI were -0.01 and -0.37 V, respectively, indicating S-mZVI possessed a stronger electron-donating ability. The practical antimony mine wastewater (C0(Sb(V)) = 3.8296 mg/L, pH = 8.29) was treated. If meeting the national discharge standard of 5 μg/L, 2.0 g/L mZVI and 1.6 g/L S-mZVI were required within 120 min. Passing N2 or reducing wastewater pH enhanced the treatment of Sb(V) by S-mZVI, in which the wastewater acidification was more effective. Once the wastewater pH was adjusted to 3.00, only 0.7 g/L S-mZVI and 40 min long time were needed to achieve the emission below 5 μg/L. Even S-mZVI underwent four cycles, and the final concentration of Sb(V) was as low as 4.67 μg/L. As the pHzpc value was 4.09 and the corrosion potential was -0.56 V at pH 3.0, the electron-donating ability of S-mZVI as well as the electrostatic attraction between the surface of S-mZVI and Sb(V) increased. Sulfidation of mZVI and then application under the acid condition significantly improved the treatment efficiency of Sb(V).

Elucidating the Fate of the Organochlorine Pesticide Chlordecone under Abiotic Reductive and Oxidative Processes: Kinetics, Transformation Products, and C vs Cl Isotope Fractionation.

Pollution of French West Indies (FWI) soils by the organochlorine pesticide chlordecone poses environmental and societal concerns due to its long-term persistence. Assessing chlordecone degradation remains challenging due to analytical constraints to identify transformation products. Here, multielement compound-specific isotope analysis (ME-CSIA) was used to identify changes in stable isotope signatures of chlordecone produced during abiotic transformation reactions under reducing and oxidative conditions. Effective chlordecone transformation was shown in reactions with zerovalent iron (ZVI), vitamin B12 and sodium sulfide (VSS), alkaline ascorbic acid (AA), and sodium persulfate activated by microwave irradiation (MWPS). Significant enrichment of 13C and 37Cl was observed in all abiotic reactions, with εC,bulk and εCl,bulk values ranging from -4.3 ± 0.4‰ to -2.3 ± 0.2‰ and from -2.6 ± 0.4‰ to -1.3 ± 0.3‰, respectively. Distinct mechanisms were evidenced in dual isotope plots, resulting in Λ values of 1.17 ± 0.28 for ZVI, 1.26 ± 0.50 for VSS, 2.06 ± 0.30 for AA, and 2.90 ± 0.50 for MWPS. Two major products were formed, 10-monohydrochlordecone and 8-monohydrochlordecone. Cl-CSIA data suggested that the first Cl substitution at the C10-position likely produced secondary Cl isotope effects (via nucleophilic substitution). Overall, results suggest that ME-CSIA can help quantify in situ chlordecone degradation, distinguishing between different ongoing degradation mechanisms and fingerprinting pollutant sources from chlordecone formulations (Curlone).

Green synthesis of nanoscale zero-valent iron impregnated walnut shell biochar as efficient adsorbent for metal(loid)s purification: Performance and mechanism insight

The escalation of metal(loid) contamination in global water poses severe risks to ecological environment safety. Meeting the ‘pollution control with waste’ strategy, we utilized eco-friendly waste tea leaf extract and walnut shell to first fabricate a greenly synthesized nanoscale zero-valent iron impregnated walnut shell biochar (G-nZVI/WSB) for the simultaneous sequestration of cadmium (Cd), lead (Pb), and arsenic (As) from aqueous systems. Since the interactions among these metal(loid)s during adsorption on G-nZVI/WSB and their corresponding mechanisms remain unclear, we conducted a series of batch experiments coupled with characterization techniques. The optimal pyrolysis temperature and Fe/C ratio for G-nZVI/WSB were determined to be 650 °C and 20 %, respectively. Under optimal conditions (contact time = 24 h, pH = 6), G-nZVI/WSB exhibited theoretical maximum adsorption capacities for Cd(II), Pb(II), and As(III) of 52.96, 135.1, and 8.414 mg g−1, respectively, which were significantly higher than those of WSB carrier. In single and combined systems, the monolayer and chemical adsorption of metal(loid)s were predominant, with their competitive affinity for active sites following the order of Pb(II) > Cd(II) > As(III). Characterization analyses using FTIR, SEM, XRD, and XPS confirmed the specific adsorption mechanisms of G-nZVI/WSB for these metal(loid)s, including cation-π interactions, coprecipitation, oxidation, and coordinated complexation. Notably, G-nZVI/WSB exhibited excellent adsorption stability over five cycles of adsorption-desorption, which achieved the efficient purification of multi-contaminated actual wastewaters to meet the standards for wastewater discharge or drinking water. These findings demonstrate the significant potential of G-nZVI/WSB as an eco-friendly and promising nanocomposite for treating metal(loid)-contaminated wastewater.

Pharmaceutical effluent degradation using hydrogen peroxide-supported zerovalent iron nanoparticles catalyst

Pharmaceutical effluents generated during drugs production and application are often times released into the water systems with little or no treatment, which could pose potential danger to the ecosystem. Advanced oxidation processes for organic pollutants treatment have gained wide consideration due to their effectiveness. In this work, hydrogen peroxide (H2O2) and hydrogen peroxide-supported nano zerovalent iron (H2O2@nZVIs) were deployed to study pharmaceutical effluents (PE) degradation via batch experiments, under various reaction time, (H2O2) and (H2O2@nZVIs) concentrations, pH, PE concentration, and temperature. The nZVIs was prepared from the green synthesis of Vernonia amygdalina leaf extract and characterized using different analytical tools such as Fourier Transform-Infrared Spectroscopy (FT-IR), Gas Chromatography Mass Spectroscopy (GC-MS), Scanning Electron Microscopy (SEM), and X-Ray Diffraction Spectroscopy (XRD). The FT-IR results showed the presence of -C = O, -NH, -OH, -C = C and, -C-O functional groups, SEM report showed that the morphology of the nZVIs is round in shape, while GC-MS revealed the presence of several phytochemicals. When the concentration of the effluent was increased from 10 to 30 ml, the percentage decolourization decreased from 74.74 to 51.96% and from 80.36 to 54.38% for H2O2 and H2O2@nZVI respectively, whereas when the contact time was increased from 10 to 60 min, the percentage decolourization rose from 70.39 to 83.49% for H2O2 and from 85.19 to 89.73% when H2O2@nZVI was used. When the effect of pH was assessed, it was observed that on increasing the pH from 2 to 10, the percentage decolourization rose from 74.5 to 80.25% for H2O2, however, with H2O2@nZVI, the percentage decolourization decreased from 81.50 to 68%. Maximum percentage decolourization of 57.10% and 94.56% for H2O2 and H2O2@nZVI was achieved at catalyst volume of 25 ml. For all the parameters tested, the H2O2@nZVIs performed much better indicating that the nZVIs enhanced the decolourization ability of the H2O2. The kinetic results showed that the decolorization of pharmaceutical effluent by both catalysts fitted very well with the second-order model, while thermodynamic properties of enthalpy change were found to be 10.025 and 27.005 kJ/mol/K for H2O2 and H2O2@nZVIs respectively suggesting that the oxidation process is endothermic in nature. This technique employed in using hydrogen peroxide-supported zero valent iron, proved to be highly efficient not only for pharmaceutical effluent degradation but also in the elimination of lead from the effluent.

Understanding Zerovalent Iron Exposure on Biological Nitrogen Removal: From Impacts to Potential Mechanisms

Understanding Zerovalent Iron Exposure on Biological Nitrogen Removal: From Impacts to Potential Mechanisms

Bisulfite enhances p-nitrophenol degradation by zero-valent iron under oxic conditions: Combination of indirect reduction by superoxide radical and direct reduction

Advanced oxidation processes based on the combination of zero-valent iron (ZVI) and S(IV) have been extensively investigated for oxidative degradation of organic pollutants, but little attention has been paid to their reducing capacities in the presence of oxygen. This work found bisulfite (BS) could greatly enhance the degradation of p-nitrophenol (PNP) by ZVI under oxic conditions and PNP was only reduced to p-aminophenol without further degradation. A combination of indirect reduction by superoxide radical (O2•–) and direct reduction by ZVI was verified as the mechanism of PNP degradation. Highly oxidizing species, such as hydroxyl radical (HO•) and sulfate radical (SO4•−), were also produced in the ZVI/BS system under oxic conditions but did not contribute to pollutant degradation perhaps due to the rapid consumption by reducing substances like BS ions and the released Fe2+. BS concentration, ZVI dosage, initial solution pH and coexisting anions (CO32–, PO43– and Cl–) affected the degradation of PNP. ZVI lost the reactivity after used for three times because of the production of goethite and lepidocrocite covered on its surface. This study will provide a new insight into degradation of organic pollutants in ZVI/BS system under oxic conditions.

A comparative study of different modification methods on zero-valent iron performance toward nitrate selective reduction to nitrogen

Although nanoscale zero-valent iron (nZVI) has been widely used for nitrate reduction, its application is always limited by the undesired generation of toxic ammonium. In this study, by selecting four commonly used nZVI modification methods (i.e., introducing Fe(II), activated carbon, Cu, and Pd), the roles of direct electron transfer and atomic hydrogen (H*) mediated reaction on nitrate selective reduction were examined. Results revealed that all the modification methods could enhance the reduction rates of nitrate with a promotion factor of 0.94–8.62, while the N2-selectivity could only be increased from ∼4.5 % to less than 25.7 % (in carbon amended system). The enhancing effect of these additives is determined to be highly associated with their ability to promote the direct electron transfer from Fe0 core to nitrate by forming galvanic couples or conductive magnetite layer. Unexpectedly, multiple lines of evidence suggested that H* was not the dominant reducing species responsible for nitrate reduction in Pd-modified nZVI system (and also the other tested systems), despite the presence of Pd could significantly accelerate H* generation. Correlation analysis further showed that there was no reasonable relationship between N2-selectivity and Fe0 corrosion tendency and hydrogen formation rates of different modified nZVI systems. All these finding could improve our understanding of nitrate selective reduction by Fe0.

Customizable Three-Dimensional Printed Zerovalent Iron: An Efficient and Reusable Fenton-like Reagent for Florfenicol Degradation.

Zerovalent iron (Fe0)-based Fenton-like technology has great potential for treating recalcitrant organic pollutants (ROPs) in wastewater. However, rapidly and precisely manufacturing Fe0-based materials with the desired geometries is challenging. Herein, novel three-dimensional printed Fe0 (3DP-Fe0) and bimetallic 3DP-Ni/Fe0 were customized by 3D printing for efficient Fenton-like degradation of florfenicol (FLO), a typical antibiotic in wastewater. 3DP-Ni/Fe0 with hydrogen peroxide (H2O2) exhibited superior reactivity toward FLO than 3DP-Fe0, generating hydroxyl radicals (·OH) and atomic hydrogen to achieve >90% dehalogenation and >70% total organic carbon removal within 10 min. The resulting degradation intermediates possessed lower antibacterial activity than FLO and did not cause resistance gene proliferation in activated sludge. The Fenton-like activity of 3DP-Ni/Fe0 was similar across different shapes but increased with increasing porosity and size. Compared with powdered Ni/Fe0, 3DP-Ni/Fe0 exhibited faster electron transfer during Fe(II)/Fe(III) cycling, which increased the utilization efficiency of dissolved Fe2+ and H2O2 for ·OH production. Moreover, 3DP-Ni/Fe0 could be reused >150 times, 5-fold more than powdered Ni/Fe0, owing to its lower metal ion release and Fe0 depletion. 3DP-Ni/Fe0 with H2O2 can also efficiently remove chemical oxygen demand from real wastewater and other ROPs (e.g., acetaminophen, carbamazepine, thiamphenicol, and tetrabromobisphenol A).

Advanced Oxidation Technology Using Fe0/H2O2 as an effective treatment for recycling industrial wastewater for irrigation of Lolium perenne crops.

This study focused on developing a new Phenton treatment of water effluent coming from a local industrial estate and staining industry site. Different advanced oxidation technologies (AOTs) such as heterogeneous photocatalysis, Photo-Fenton and UV-Vis/H2O2 using FeSO4, and pure iron were evaluated. To develop this study, water samples were tested before and after each treatment. In general, after AOTs the amount of chlorides, nitrates, hydrocarbons, heavy metals, TOC and bacteria significantly decreased. Photo-Fenton and UV-Vis/H2O2/TiO2 showed the best performance in the treatment of staining industry and industrial wastewater, respectively. Photo-Fenton mineralized 100% of dyes, reduced by 99% total coliforms, eliminated 76% of TOC and 60% of heavy metals tested. Interestingly, use of iron metal in the Photo-Fenton treatment was found to achieve similar results. This means wastewater can be treated with benign chemicals. Treated wastewater was evaluated as a potential water source for the irrigation of Lolium perenne, a conventional crop in animal feed. In general, the physical characteristics of Lolium perenne such as leaf and roof length and width, were not significantly modified after irrigation with treated wastewater. Similar results were obtained using treated tap water as reference. A trace number of metals remaining from treatment was detected in grass and soil. However, the concentration of Cd, Cr, Cu, and Zn was very similar to tap water. Considering these outcomes, use of non-toxic zero valent iron metal and hydrogen peroxide in a Photo-Fenton reaction is a pilot plant scalable alternative oxidating treatment technology for recycling industrial wastewater in agricultural activities.Top of Form

Adsorptive removal of Fe and Cd from the textile wastewater using ternary bio-adsorbent: adsorption, desorption, adsorption isotherms and kinetic studies

Ternary bio-adsorbent was synthesized by using sisal fiber as a base with the integration of conductive polymer; polyaniline (PANI), supported with zero-valent iron nanoparticles by chemical activation with potassium hydroxide. The activation temperature impact on adsorption properties of Sisal fiber composite activated carbon was studied. The activation temperatures had a major effect on adsorption process as 100% removal efficiency was attained at 800 °C activated temperature. Scanning electron microscopy (SEM) was used for surface analysis of the adsorbent. Adsorption isotherms (Langmuir, Freundlich and Temkin) were examined and the negative values of 1/nF\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$1/n_{F}$$\\end{document} demonstrated that the adsorption data does not match with Freundlich model for chemisorption. The pseudo second order and Elovich kinetics correlation coefficients for the retention of Fe and Cd to solid-phase interface at SF-800/NP/PANI (C) offered a better correlation for the bio-adsorption of Fe and Cd than pseudo first order kinetic. However, the pseudo second order kinetic attained a surpassing interaction for the bio-adsorption of Fe (0.989) than Cd (0.966); while the Elovich kinetic attained a surpassing interaction for the bio-adsorption of Cd (0.975) than Fe (0.945). The recovery and recycling stability of the bio-adsorbent composites were studied.

Enhanced anaerobic digestion for energy recovery from brewery wastewater employing nano zero-valent iron loaded biochar prepared by residual sludge

Anaerobic digestion is an effective wastewater energization technology, but suffers from low energy conversion efficiency. In this study, a novel biochar was successfully prepared by incorporating extracellular polymeric substances (EPS) to residual sludge, and the anaerobic digestion performance could be significantly improved by employing this biochar loaded with nano zero-valent iron (NZVI@EPSBC). In comparison to the control, the cumulative methane production with 100 mg/L NZVI@EPSBC was raised by approximately 1.4-fold. The NZVI@EPSBC did not significantly change the morphology of the inoculated granular sludge, but induced the secretion of proteins and humic substances in the extracellular EPS, which are beneficial for carbon conversion and extracellular electron transport at the microscopic scale. Meanwhile, the quantitative analysis of the electron transport system also confirmed that NZVI@EPSBC could significantly improve the electron transfer efficiency in microbial respiratory chain throughout the experimental cycle, in which the highest respiratory efficiency increase of 26.51 % at 48 h. Taxonomic analysis of microbial communities showed that NZVI@EPSBC exhibited complete retention of bacteria and archaea compared to the raw sludge, while realizing an efficient cooperative pattern of syntrophic bacteria by regulating the relative abundance of specific functional bacteria, like Anaerolineaceae and Methanosaeta. Overall, the study offers a valuable strategy for achieving resourcefulness of residual sludge and EPS along with facilitating efficient energy recovery from brewery wastewater.

Electrocatalytic Nitrate Reduction for Brackish Groundwater Treatment: From Engineering Aspects to Implementation

In recent years, nitrate has emerged as a significant groundwater pollutant due to its potential ecotoxicity. In particular, nitrate contamination of brackish groundwater poses a serious threat to both ecosystems and human health and remains difficult to treat. A promising, sustainable, and environmentally friendly solution when biological treatments are not applicable is the conversion of nitrate to harmless nitrogen (N2) or ammonia (NH3) as a nutrient by electrocatalytic nitrate reduction (eNO3R) using solar photovoltaic energy. This review provides a comprehensive overview of the current advances in eNO3R for the production of nitrogen and ammonia. The discussion begins with fundamental concepts, including a detailed examination of the mechanisms and pathways involved, supported by Density Functional Theory (DFT) to elucidate specific aspects of ammonium and nitrogen formation during the process. Furthermore, the integration of artificial intelligence (AI) and machine learning (ML) offers promising advancements in enhancing the predictive power of DFT, accelerating the discovery and optimization of novel catalysts. In this review, we also explore various electrode preparation methods and emphasize the importance of in situ characterization techniques to investigate surface phenomena during the reaction process. The review highlights numerous examples of copper-based catalysts and analyses their feasibility and effectiveness in ammonia production. It also explores strategies for the conversion of nitrate to N2, focusing on nanoscale zerovalent iron as a selective material and the subsequent oxidation of the produced ammonia. Finally, this review addresses the implementation of the eNO3R process for the treatment of brackish groundwater, discussing various challenges and providing reasonable opinions on how to overcome these obstacles. By synthesizing current research and practical examples, this review highlights the potential of eNO3R as a viable solution to mitigate nitrate pollution and improve water quality.