Efficient remediation of different concentrations of Cr-contaminated soils by nano zero-valent iron modified with carboxymethyl cellulose and biochar.

Nano zero-valent iron (nZVI) is widely used in soil remediation due to its high reactivity. However, the easy agglomeration, poor antioxidant ability and passivation layer of Fe-Cr coprecipitates of nZVI have limited its application scale in Cr-contaminated soil remediation, especially in high concentration of Cr-contaminated soil. Herein, we found that the carboxymethyl cellulose on nZVI particles could increase the zeta potential value of soil and change the phase of nZVI. Along with the presence of biochar, 97.0% and 96.6% Cr immobilization efficiency through CMC-nZVI/BC were respectively achieved in high and low concentrations of Cr-contaminated soils after 90-days remediation. In addition, the immobilization efficiency of Cr(VI) only decreased by 5.1% through CMC-nZVI/BC treatment after 10 weeks aging in air, attributing to the strong antioxidation ability. As for the surrounding Cr-contaminated groundwater, the Cr(VI) removal capacity of CMC-nZVI/BC was evaluated under different reaction conditions through column experiments and COMSOL Multiphysics. CMC-nZVI/BC could efficiently remove 85% of Cr(VI) in about 400 hr when the initial Cr(VI) concentration was 40 mg/L and the flow rate was 0.5 mL/min. This study demonstrates that uniformly dispersed CMC-nZVI/BC has an excellent remediation effect on different concentrations of Cr-contaminated soils.

Pristine/magnesium-loaded biochar and ZVI affect rice grain arsenic speciation and cadmium accumulation through different pathways in an alkaline paddy soil.

Cadmium (Cd) and arsenic (As) co-contamination has threatened rice production and food safety. It is challenging to mitigate Cd and As contamination in rice simultaneously due to their opposite geochemical behaviors. Mg-loaded biochar with outstanding adsorption capacity for As and Cd was used for the first time to remediate Cd/As contaminated paddy soils. In addition, the effect of zero-valent iron (ZVI) on grain As speciation accumulation in alkaline paddy soils was first investigated. The effect of rice straw biochar (SC), magnesium-loaded rice straw biochar (Mg/SC), and ZVI on concentrations of Cd and As speciation in soil porewater and their accumulation in rice tissues was investigated in a pot experiment. Addition of SC, Mg/SC and ZVI to soil reduced Cd concentrations in rice grain by 46.1%, 90.3% and 100%, and inorganic As (iAs) by 35.4%, 33.1% and 29.1%, respectively, and reduced Cd concentrations in porewater by 74.3%, 96.5% and 96.2%, respectively. Reductions of 51.6% and 87.7% in porewater iAs concentrations were observed with Mg/SC and ZVI amendments, but not with SC. Dimethylarsinic acid (DMA) concentrations in porewater and grain increased by a factor of 4.9 and 3.3, respectively, with ZVI amendment. The three amendments affected grain concentrations of iAs, DMA and Cd mainly by modulating their translocation within plant and the levels of As(III), silicon, dissolved organic carbon, iron or Cd in porewater. All three amendments (SC, Mg/SC and ZVI) have the potential to simultaneously mitigate Cd and iAs accumulation in rice grain, although the pathways are different.

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.

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.

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.

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

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

Roles of silica coating on nanosized zero-valent iron in sequential reduction-oxidation process in a system containing persulfate.

A sequential reduction-oxidation process using silica-coated nanosized zero-valent iron (nZVI) particles (nZVI@SiO2) and persulfate for mineralizing recalcitrant compounds was developed, and the effects of the process on nitrobenzene were evaluated. This sequential process significantly enhanced contaminant mineralization, which could not be effectively achieved by reduction or oxidation alone. The nZVI@SiO2 rapidly reduced nitrobenzene to aniline, then the aniline concentration gradually decreased after persulfate had been added and initiated sequential oxidative degradation. The SiO2 coating on the nZVI@SiO2 limited outward mass transfer of reaction products and increased the efficiency with which nitrobenzene was converted into aniline. Slow release of Fe(II) caused by the coating caused persulfate activation and subsequent aniline oxidation to be more sustained and efficient than without the coating. The final nitrobenzene-aniline mineralization efficiency was higher for the nZVI@SiO2/persulfate system than the nZVI/persulfate system. The SiO2 coating of the nZVI@SiO2 particles was an excellent protective layer, protecting the particles from undesirable consumption through reactions with groundwater components. nZVI@SiO2 particle transformations during the sequential process were investigated, and the operating conditions were optimized to maximize the recalcitrant compound removal efficiency. The results indicated that nZVI@SiO2 and persulfate could be used to mineralize organic contaminants in groundwater through sequential reduction-oxidation.

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

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

A novel strategy for enhancing high solid anaerobic digestion of fecal slag and food waste using percolate recirculation and dosage of nano zero-valent iron.

To speed up reaching UN Sustainable Development Goal 6 for safe sanitation by 2030, integrating high-solid anaerobic digestion (HSAD) into decentralized systems could recycle fecal slag (FS) and food waste (FW), aiding a circular economy and toilet revolution. In this study, a percolate recirculation system and conductive material were used to improve mass transfer, stability, and enhance methane production in HSAD of FS and FW. This setup consists of a percolate tank and a digester tank, where nano-zero valent iron (nZVI) was dosed in the percolate tank (PnZVI in P) and the digester tank (PnZVI in D) and compared with a control with no additive (PControl). The highest cumulative methane yield of 519.43 mL/gVS was achieved in PnZVI in D, which was 4.52 and 3.59 times higher than that of PControl (144.59 mL/gVS) and PnZVI in P (114.96 mL/gVS). This finding demonstrates that the dosing strategy of PnZVI in D facilitated effective interaction among organic matter, microbial communities, and nZVI, resulting in organics removal efficiencies of 67.42 % (total solid) and 77.22 % (volatile solid). Moreover, microbial community analysis supported the efficacy of the PnZVI in D strategy, revealing the enrichment of Clostridium sensu stricto 1 (46.91 %), which potentially engaged in interspecies electron transport (Interspecies hydrogen transfer (IHT) and direct interspecies electron transfer (DIET)) with Methanobacterium (81.19 %) and Methanosarcina (17.11 %). These interactions contribute to enhanced methane yield and stability maintenance in the HSAD system with percolate recirculation. The findings of this study demonstrate that the implementation of HSAD of FS and FW, coupled with percolate recirculation and the addition of nZVI, holds promise for enabling sustainable sanitation practices in developing regions. Moreover, this approach not only facilitates resource recovery but also eliminates the requirement for water.

Rapid and efficient removal of organophosphorus pollutant and recovery of valuable elements: A boosted strategy for eliminating organophosphorus from wastewater.

Considering the significant hazards of organophosphorus compounds (OPs) and the potential crisis of phosphorus (P) resource shortage, there is a great necessity to develop economically feasible, highly effective, and sustainable strategies to remove OPs and recover P resources. In this study, low-cost microscale zero-valent iron (mZVI) was used to activate hydrogen peroxide for the rapid and efficient elimination of Tetrakis(hydroxymethyl)phosphonium sulfate (THPS) from the aquatic environment. Compared to the conventional Fenton reaction and commercial mZVI, mZVI/H2O2-based Fenton-like reaction exhibited superior removal performance for THPS. The removal mechanism of the mZVI/H2O2 system for THPS was thoroughly elucidated through the identification of reactive oxygen species, characterization analysis, and theoretical calculation. Furthermore, the valuable components of the degradation products were successfully recovered through thermally induced precipitation of the sample followed by high-temperature calcination. The mZVI/H2O2 system has demonstrated significant advantages in removing organic compounds from various types of actual wastewater and improving the biodegradability of the wastewater. This study presented an environmentally friendly and highly efficient strategy to eliminate OPs pollution and recover P resources. It also provided an easy-to-operate method for remediating actual industrial wastewater.

Sulfidation of Nanoscale Zero-Valent Iron by Sulfide: The Dynamic Process, Mechanism, and Role of Ferrous Iron.

Sulfidation of nanoscale zerovalent iron (nZVI) can enhance particle performance. However, the underlying mechanisms of nZVI sulfidation are poorly known. We studied the effects of Fe2+ on 24-h dynamics of nZVI sulfidation by HS- using a dosed S to Fe molar ratio of 0.2. This shows that in the absence of Fe2+, HS- rapidly adsorbed onto nZVI particles and reacted with surface iron oxide to form mackinawite and greigite (<0.5 h). As nZVI corrosion progressed, amorphous FeSx in solution deposited on nZVI, forming S-nZVI (0.5-24 h). However, in the initial presence of Fe2+, the rapid reaction between HS- and Fe2+ produced amorphous FeSx, which deposited on the nZVI and corroded the surface iron oxide layer (<0.25 h). This was followed by redeposition of colloidal iron (hydr)oxide on the particle surface (0.25-8 h) and deposition of residual FeSx (8-24 h) on S-nZVI. S loading on S-nZVI was 1 order of magnitude higher when Fe2+ was present. Surface characterization of the sulfidated particles by TEM-SAED, XPS, and XAFS verified the solution dynamics and demonstrated that S2- and S22-/Sn2- were the principal reduced S species on S-nZVI. This study provides a methodology to tune sulfur loading and S speciation on S-nZVI to suit remediation needs.

Enhanced the removal of norfloxacin by oxalated zero-valent iron with rich surface Fe(II) sites activating the chlorite.

Oxalic acid-modified ball-milled zero-valent iron (OA-ZVIbm) was employed to activate sodium chlorite (ClO2-) for the removal of norfloxacin (NOR). The complete removal of 20 mg/L NOR was achieved within 60 min by the OA-ZVIbm/ClO2- process. Compared with the ZVIbm/ClO2- process which was the ball-milled zero-valent iron (ZVIbm) activate sodium chlorite, the reaction activity of the OA-ZVIbm/ClO2- process was increased by 102.6 times. Through scanning electron microscopy (SEM), X-ray photoelectron spectroscopy (XPS), electrochemical testing, and density functional theory (DFT) calculations, which has been confirmed that the introduction of oxalic acid can significantly increase the surface Fe(II) content of OA-ZVIbm, and accelerate the electron transfer rate of iron nuclei, thereby improve the efficiency of ClO2- activation for the removal of NOR. The role of various active species in NOR removal, which were •O2-, 1O2, Fe(IV), ClO2, and •OH, was elucidated through free radical quenching experiments, electron paramagnetic resonance (EPR) spectroscopy, and quantitative detection of active species. These active species all participated in the reaction, while •O2- played a dominant role in the reaction because it could transform into other active species, such as (•OH, 1O2). Inorganic anions and natural organic matter have no significant effect on the removal of NOR in the OA-ZVIbm/ClO2- process. The protonation of oxalic acid ensured its good pH applicability range (pH = 2-11), thus exhibiting excellent performance in NOR removal in real water bodies. This further demonstrates that OA-ZVIbm prepared by oxalic acid ball milling modification is an efficient ClO2- activator, offering promising prospects for antibiotic removal technology.

Filters comprised of sand and Zero Valent Iron hold promise as tools to mitigate risk posed by Cyclospora cayetanensis oocysts.

Irrigation water contaminated by human fecal material may elevate the risk of produce contamination with the enteric parasite Cyclospora cayetanensis. Oocysts of C. cayetanensis are resistant to commonly used disinfectants and a method of removing C. cayetanensis from irrigation water would mitigate this risk. We evaluated zero valent iron (ZVI) sand filtration as one such method. We sought to determine if sand filters containing ZVI outperformed those without ZVI. We first evaluated the abundant poultry parasites Eimeria maxima, E. tenella and E. acervulina as surrogates for C. cayetanensis. We determined if a miniaturized gravity fed ZVI-sand filter, scaled to evaluate scarce supplies of C. cayetanensis oocysts, provided useful information about the performance of larger filtration systems. Filters were inoculated with oocysts, rinsed, and the resulting filtrate examined microscopically for oocysts. We performed experiments to measure the effect of varying ZVI concentrations, repeated filter use, simulated agricultural water, and oocyst size and condition. We then compared the performance of mini filters to that of larger, gravity-fed pool filters and found that ZVI-sand filtration was far more effective at removing Eimeria spp. from water when compared to sand filtration, at both scales. Sand mini filters retained 13-54 % of E. acervulina oocysts, and pool filters retained 82 %, but when combined with 50 % (mini filter) or 35 % (pool filter) v/v ZVI, mini filters retained 89-99 % of oocysts and pool filters retained >99 %. The effectiveness of the mini filters increased with increasing ZVI concentration, and the addition of ZVI far outweighed the influence of any other measured variable. We then performed experiments including C. cayetanensis, which provided similar results to those utilizing Eimeria; 59 % of inoculated C. cayetanensis oocysts were retained in sand mini filters, and 97 % in mini filters composed of 35 % v/v ZVI. In sum, ZVI is highly effective in removing oocysts from water and Eimeria is a useful surrogate for C. cayetanensis to assess filtration. ZVI-sand filtration shows promise as a tool to mitigate the risk of C. cayetanensis contamination of irrigation water. Further studies should evaluate the performance of ZVI-sand in pressurized fast filtration systems under a range of field conditions.

Nanoscale zero-valent iron alleviated horizontal transfer of antibiotic resistance genes in soil: The important role of extracellular polymeric substances.

Extracellular polymeric substances (EPS) are tightly related to the horizontal gene transfer (HGT) of antibiotic resistance genes (ARGs), but often neglected in soil. In this study, nanoscale zero-valent iron (nZVI) was utilized for attenuation of ARGs in contaminated soil, with an emphasis on its effects on EPS secretion and HGT. Results showed during soil microbe cultivation exposed to tetracycline, more EPS was secreted and significant increase of tet was observed due to facilitated HGT. Notably, copies of EPS-tet accounted for 71.39 % of the total tet, implying vital effects of EPS on ARGs proliferation. When co-exposed to nZVI, EPS secretion was decreased by 38.36-71.46 %, for that nZVI could alleviate the microbial oxidative stress exerted by tetracycline resulting in downregulation of genes expression related to the c-di-GMP signaling system. Meanwhile, the abundance of EPS-tet was obviously reduced from 7.04 to 5.12-6.47 log unit, directly causing decrease of total tet from 7.19 to 5.68-6.69 log unit. For the reduced tet, it was mainly due to decreased EPS secretion induced by nZVI resulting in inhibition of HGT especially transformation of the EPS-tet. This work gives an inspiration for attenuation of ARGs dissemination in soil through an EPS regulation strategy.

Enhancing pakchoi cabbage yield and quality but reducing human-disease risk of bacterial community from wastewater irrigation by combined nanoscale zerovalent iron and nitrification inhibitor.

It was indispensable to seek effective and feasible measures to alleviate the adverse effects of wastewater irrigation. Nanoscale zerovalent iron (nZVI) and soil nitrogen management might enhance the vegetable yield and quality but mitigate the potential human-disease risks from wastewater irrigation. This study selected the nZVI and nitrification inhibitor as experimental objects. The planted pakchoi cabbage was irrigated with the tap water and wastewater and treated with nZVI and 3, 4-dimethylpyrazole phosphate (DMPP), respectively, the pakchoi cabbage yield and quality, soil enzyme activity and abiotic property, and human-disease risk of bacterial community were quantified. Compared with the control, the nZVI significantly enhanced the pakchoi cabbage yield by 51.5% but reduced the pakchoi cabbage nitrate content by 52.6% under wastewater irrigation condition. The nZVI alone had double-edged sword effects of increasing the pakchoi cabbage yield, reducing the pakchoi cabbage nitrate content and soil human-disease risk but inhibiting the system multifunctionality and soil bacterial community diversity and stability, under wastewater irrigation condition. The nZVI diminished human-disease risk via increasing the soil Firmicutes and Verrucomicrobiota ratios, and the extra DMPP could mitigate the negative effects of nZVI by increasing soil enzyme activity and stimulating soil Acidobacteria ratio. The combinations of nZVI and DMPP could not only enhance the pakchoi cabbage yield and quality but also reduce the human-disease risk of soil bacterial community from wastewater irrigation.

Chemical aging of biochar-zero-valent iron composites in groundwater: Impact on Cd(II) and Cr(VI) co-removal.

Biochar (BC), zero-valent iron (ZVI), and their composites are promising materials for use in permeable reactive barriers, although further research is needed to understand how their properties change during long-term aging in groundwater. In this study, BC, ZVI and their composites (4BC-1ZVI) were subjected to the chemical aging tests in five media (deionized water, NaCl, NaHCO3, CaCl2 and a mixture of CaCl2 and NaHCO3 solutions) for 20 days. After treatment, the microscopic analysis and performance tests for the co-removal of Cd(II) and Cr(VI) were carried out. The results indicated that the removal of Cd(II) by aged 4BC-1ZVI followed a pseudo-second-order model, whereas the removal of Cr(VI) was better fitted with a pseudo-first order model. The aging mechanism of 4BC-1ZVI was primarily governed by iron corrosion/passivation, the reduction of soluble components, and the formation of carbonate minerals. Less Fe3O4/ γ-Fe2O3 was formed during aging in deionized water, NaCl and CaCl2 solutions. The corrosion products, Fe3O4/ γ-Fe2O3, FeCO3 and α/γ-FeOOH, were observed after aging in NaHCO3 and a mixture of NaHCO3 and CaCl2 solutions. The decrease in the soluble components of biochar led to a decrease in cation exchange, while carbonate minerals contributed to Cd(II) precipitation. This work provides insights into the aging processes of BC-ZVI composites for long-term groundwater remediation applications.

Effective hydrogen production and coupling degradation of organics (4-nitrophenol, methylene blue, and Rhodamine B) in wastewater by electrospun PAN@Fe0 composite nanofibers.

The pursuit of clean energy generation and environmental preservation is of utmost importance for societal progress. However, couple clean energy production and pollution control is still a difficulty. In this study, a novel electrospun composite mat, with nano zero valent iron (Fe0, nZVI) encapsulated into polyacrylonitrile (PAN) nanofibers was acted as a catalyst. The activation energy (Ea) for the hydrolysis of NaBH4 to produce hydrogen is 22 kJ·mol-1, hydrogen atom utilization efficiency (HGE) of NaBH4 is 60.80%. Three kinds of organic dyes 4-nitrophenol (4-NP), methylene blue (MB), and Rhodamine B (RhB) were served as the model pollutant, to construct NaBH4-organic system for energy production and pollution reduction. The NaBH4-organic system demonstrates a collaborative capability to simultaneously remove organic pollutants and generate hydrogen, with a coupling equilibrium point between the two processes. The hydrogen generation rate (HGR) and HGE increased with the concentration of pollutants increased. The degradation of 4-NP, MB, and RhB followed pseudo-first-order kinetics, with RhB degrading dosage 20 and 44 times higher than 4-NP and MB, respectively. H2 and H· contributed to the organic degradation. nZVI directly participated in the formation H2 and H·. PAN@Fe0 possessed good recyclability and moderate cost. The degradation process adhered to the classical surface reaction controlled Langmuir-Hinshelwood (L-H) model. The integration of synergistic production capacity and pollutant degradation aligns well with the principles of green chemistry and sustainable development. This study demonstrates a novel approach to no precursor loss catalysts preparation, efficient production clean H2, advanced treatment of dye-containing wastewater, carbon neutral operation of sewage treatment plant.

Experimental study on harmful effects of zero-valent Iron on Paraprionospio patiens.

Iron is an essential trace element for living organisms, and it plays an important role in redox reactions in aquatic environments. Although many studies have investigated the application of iron materials to improve water and sediment quality, their negative effects remain unknown. Therefore, this study investigated the effects of three iron materials, i.e., zero-valent iron, iron oxide, and iron oxyhydroxide, on common benthic organisms in a coastal area via exposure experiments. In the exposure experiments, Paraprionospio patiens, a marine polychaete, exhibited abnormal behavior immediately after the addition of zero-valent iron, and the average survival rate after 14 d decreased significantly (Scheffé's test: p < 0.05). This is the first study to show that zero-valent iron on the sediment surface negatively affects the survival of P. patiens. Although Iron materials are often used to improve aquatic environments, their potential adverse effects should be addressed through continuous monitoring after use.

Bioconversion of pure CO2 to caproic acid with zero valent iron: Optimizing carbon flux distribution in co-cultures of Acetobacterium woodii and Megasphaera hexanoica.

Acetobacterium woodii and Megasphaera hexanoica were co-cultured for caproic acid (CA) production from lactic acid (LA) and CO2. Also, various concentrations (1 g/L, 3 g/L, 5 g/L, and 10 g/L) of Zero Valent Iron (ZVI) were supplied to study its impact on the co-culture system. In flask experiments, 10 g/L LA and 1.0 bar CO2 produced 0.6 g/L CA with some biomass growth. ZVI increased LA consumption and CA production. Indeed, 3 g/L ZVI boosted CA production by 186 % and biomass accumulation by 103 %, suggesting that ZVI controls the carbon flux. Subsequent automated bioreactor studies showed that 3 g/L ZVI produced 1.842 g/L CA at stable pH, compared to 0.969 g/L without ZVI (control). Further, metabolic activity showed that both bacteria could directly use H2, generated by ZVI (3 g/L), as electron donor. Higher ZVI concentrations (10 g/L) resulted in Fe2+ causing excessive oxidation pressure on M. hexanoica, with its carbon flux flowing preferentially towards biomass. Enzyme assays confirmed that A. woodii preferred 10 g/L ZVI while M. hexanoica preferred 3 g/L for optimal bioconversion.

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.