Nano Zero-valent Iron Research Articles

Bio-inspired adsorption sheets from waste material for anionic methyl orange dye removal

Nano zero-valent iron (nZVI), bimetallic nano zero-valent iron-copper (Fe0–Cu), and Raw algae (sargassum dentifolium) activated carbon-supported bimetallic nano zero-valent iron-copper (AC-Fe0–Cu) are synthesized and characterized using FT-IR, XRD, and SEM. The maximum removal capacity is demonstrated by bimetallic activated carbon AC-Fe0–Cu, which is estimated at 946.5 mg/g capacity at the condition pH = 7, 30 min contact time under shaking at 120 rpm at ambient temperature, 200 ppm of M.O, and 1 g/l dose of raw algae-Fe0–Cu adsorbent. The elimination capability of the H3PO4 chemical AC-Fe0–Cu adsorbent is 991.96 mg/g under the conditions of pH = 3, 120 min contact time under shaking at 120 rpm at room temperature, 200 ppm of M.O, and 2 g/l doses of H3PO4 chemical AC-Fe0–Cu adsorbent. The Bagasse activated carbon adsorbent sheet achieves a removal capacity of 71.6 mg/g MO dye solution. Kinetic and isothermal models are used to fit the results of time and concentration experiments. The intra-particle model yields the best fit for bimetallic Fe0–Cu, AC-Fe0–Cu, H3PO4 chemical AC-Fe0–Cu and bagasse activated carbon(CH), with corrected R-Squared values of 0.9656, 0.9926, 0.964, and 0.951respectively. The isothermal results emphasize the significance of physisorption and chemisorption in concentration outcomes. Response surface methodology (RSM) and artificial neural networks (ANN) are employed to optimize the removal efficiency. RSM models the efficiency and facilitates numerical optimization, while the ANN model is optimized using the moth search algorithm (MSA) for optimal results.HighlightsThe Fe0–Cu composite, when combined with activated carbon from Bagasse Pulp (CH), exhibited the most effective decolorization effectiveness for anionic colours present in wastewater.The utilization of composites presents a promising opportunity for efficient dye removal due to its cost-effectiveness and environmentally sustainable nature. The utilization of response surface approach and artificial neural network modelling improves the efficacy of removal processes and treatment techniques.

Efficient degradation of phenanthrene by biochar-supported nano zero-valent iron activated persulfate: performance evaluation and mechanism insights.

Biochar-supported nano zero-valent iron (BC@nZVI) is a novel and efficient non-homogeneous activator for persulfate (PS). This study aimed to identify the primary pathways, the degradation mechanism and the performance of phenanthrene (PHE) with PS activated by BC@nZVI (BC@nZVI/PS). BC@nZVI as an activator for PS was prepared by liquid phase reduction method. BC@nZVI was characterized using scanning electron microscopy, transmission electron microscopy, X-ray diffractometer and Fourier transform infrared spectroscopy. The effects of the iron-carbon mass ratio and BC@nZVI dosage were investigated, and a pseudo-first-order kinetic model was used to evaluate the PHE degradation. The results showed that BC supported nZVI and inhibited the agglomeration of nZVI, improving PS's activation efficiency. The optimal iron-carbon mass ratio was determined to be 1:4, accompanied by a dosage of 0.6 g/L of BC@nZVI. During PS activation, nZVI was transformed to Fe2+ and Fe3+, with the majority being Fe3+. The reducibility of nZVI in BC@nZVI enabled the reduction of Fe3+ to Fe2+ to activate PS. Radical quenching and electron paramagnetic resonance (EPR) revealed that the oxidative radicals in the BC@nZVI/PS system were mainly SO4-· and ·OH, where SO4-· was the primary free radical under acidic and neutral conditions and ·OH in alkaline conditions.Additionally, BC@nZVI adsorption had a limited role in PHE removal. This study can provide mechanism insights of PHE degradation in water with BC@nZVI activation of the Na2S2O8 system.

Molybdate modified nano zero-valent iron via green synthesis enhances Cr(VI) reduction during their cotransport in water-saturated porous media

The in situ remediation of hexavalent chromium (Cr(VI)) pollution in groundwater and soil using nano zero-valent iron (nZVI) has garnered great attention. However, Cr(VI) remediation, particularly its reduction remains limited in the subsurface due to the poor migration of nZVI materials to contaminated sites. Herein, we successfully prepared a series of Mo/nZVI@GT materials with varying Mo/Fe synthesis molar ratios using green tea extracts and molybdate and efficiently improved the transportability of Mo/nZVI@GT. The pronounced size-selective retention of Mo/nZVI@GT in water-saturated porous media also favors for the effective reaction with Cr(VI) during their cotransport. Moreover, Cr(VI) reduction capacity of Mo/nZVI@GT was remarkably improved at pH 6.0, especially in the presence of phosphate. Mechanistically, X-ray absorption near-edge spectroscopy (XANES) and X-ray photoelectron spectroscopy (XPS) revealed that tea polyphenols promoted the production of Mo(IV) species in Mo/nZVI@GT, which enhanced the conversion of Cr(VI) to Cr2O3 rather than Cr(OH)3. Additionally, the increased Mo(IV) and Fe(II) active sites might mitigate phosphate disturbance. This study elucidated the mechanisms of Cr(VI) reduction and removal by green synthesized nZVI@GT with Mo modification during their cotransport and highlighted the potential application of Mo/nZVI@GT composites in efficient in situ remediation of Cr(VI)-contaminated groundwater and soil.

Boron-doped biochar-nano loaded zero-valent iron to activate persulfate for the degradation of oxytetracycline

Oxytetracycline has posed a serious environmental nuisance, and seeking environmental decontamination materials is the priority task to deal with antibiotic water contamination. Herein, boron-doped biochar loaded nano zero-valent iron composites (nZVI/BBC) were fabricated as activators of PDS for oxidative degradation of oxytetracycline hydrochloride (OTC), and the main removal mechanism was explored in detail. The results showed that Boron-doped biochar with borate ester structure (BC2O) and degree of defects are the main active sites for improving PDS activation properties. BBC could effectively prevent nZVI agglomeration and reduce nZVI passivation. The effects of calcination temperature of BBC, loading ratio and dosage of nZVI/BBC, PDS concentration, initial solution pH, pollutant concentration, and interfering ions on OTC removal by nZVI/BBC were also systematically investigated, and the optimal reaction conditions were screened: 10 wt% loading of nZVI in the composite, 1 g/L dosage of nZVI/BBC, 1 mM dosage of PDS and solution pH= 5. The cycling test showed that the removal rate of OTC by nZVI/BBC decreased from 95.3% to 70.2% after five cycles, indicating that there is excellent stability of this material. Among them, the catalyst of 10%nZVI/BBC displayed the optimal PDS activation performance, owing to the synergistic adsorption-double oxidation system, BBC as well as nZVI. The free radical quenching experiment and free radical trapping experiment proved that the degradation of OTC mainly followed the free radical pathway and SO4•− and •OH were the primary active species in the catalytic system. This study provides a practical reference for the treatment of actual antibiotic wastewater.

Performance evaluation of sulfidated nanoscale iron for hexavalent chromium removal from groundwater in sequential batch study.

Chromium [Cr] contamination in groundwater is one of the serious environmental concerns due to the carcinogenicity of its water-soluble and mobile hexavalent [Cr(VI)] form. In spite of the existence of multiple precipitation and adsorption-based Cr(VI) remediation technologies, the usage of sulfidated nano zerovalent iron (S-nZVI) has recently attracted researchers due to its high selectivity. Although S-nZVI effectively immobilized Cr(VI), its long-term performance in multiple shifted equilibrium has not been explored. In this contribution, influences of S-nZVI dosage, initial concentration of Cr(VI), pH, ionic strength, total hardness, sulfate, carbonate, and silicate were probed in ultrapure water. Further experiments were performed in synthetic groundwater to investigate the effects of initial concentration of Cr(VI) in the pH range of 4-8 for 1g L-1 S-nZVI dosage. Cr(VI) removal rate was quantified in groundwater without pH fixation. Finally, a comparative study between conventional nano zerovalent iron (nZVI) and S-nZVI was conducted in sequential batch reactors to investigate their respective efficiencies during repeated usage. Mechanistic interpretation of the processes governing the immobilization of Cr(VI) was done by integrating the results of these experiments with the metadata. While aggregation due to magnetic properties and rapid oxidation of Fe decreased the efficiency of nZVI with repeated usage, sulfidation minimized the passivation and favored an extended reducing environment because of continuous electron transfer from iron and sulfur components.

Long-term impact of nano zero-valent iron on methanogenic activity, microbial community structure, and transcription activity in anaerobic wastewater treatment system

Nano zero-valent iron (NZVI) is commonly used in industrial wastewater treatment. However, its long-term impact mechanisms of metabolization in anaerobic systems are not well understood. This study investigated the effects of long-term and continuous addition of NZVI on methanogenic activity, microbial community, and transcription activity. The results demonstrated that low levels of NZVI (1000 mg/L) induced inhibition of methanogenesis after 80 days, while high levels of NZVI (5000 mg/L) immediately led to a sharp decrease of cumulative methane production and chemical oxygen demand removal, which arrived at a steady state (14.4 % of control and 17 %) after 30 days. NZVI adversely affected cell viability, adenosine triphosphate production, and fatty acid evolution of cell membranes played a crucial role in resisting chronic NZVI toxicity. Moreover, high NZVI levels hindered the transcription of key enzymes CoM and mcrA, while low NZVI levels maintained its high CoM and mcrA activity, but down-regulated the transcription of cdh and hdr. Besides, amino-utilizing bacteria was reduced under the high NZVI concentration, while low NZVI changed dominant genus with potential protein hydrolysis function from Candidatus Cloacamonas to Sedimentibacter. These results provide a guideline for proper NZVI utilization in wastewater treatment.

Synergistic effect and mechanism of nZVI/LDH composites adsorption coupled reduction of nitrate in micro-polluted water

In this study, nZVI/LDH composites were prepared by loading nano zero-valent iron (nZVI) on layered double hydroxide (LDH) surface for adsorption coupled reduction of nitrate (NO3--N). The results showed that the removal of NO3--N and total nitrogen (TN) by the nZVI/LDH composites was 88.64% and 77.63%, respectively, with a selectivity of 55.21% for N2 and only 1.86% for ammonia nitrogen (NH4+-N) within 180 min. The valence states of various N forms during the adsorption-reduction process were investigated. The mechanism of synergistic adsorption-reduction degradation of NO3--N was proposed by measuring the contents of NO3--N, nitrite (NO2--N), and NH4+-N in the aqueous and adsorbed phases in the reaction process, including rapid adsorption of initial NO3--N, chemical reduction of adsorbed NO3--N and resorption of the final product. The nZVI/LDH also maintained up to 82.56% NO3--N removal in natural water, with aging experiments proved that the composites maintained 60.48% NO3--N removal after 15 days. Therefore, the composites may have great application prospects for NO3--N removal in micro-polluted water.

Synergistic effect and interaction of nano zero-valent iron and Al13 in carbamazepine removal

In this study, a multi-functional coagulant with both coagulation and oxidation function was obtained by pre-doped nano zero-valent iron (nZVI) with Al13 for the removal of the typical emerging contaminants Carbamazepine (CBZ). At the optimal doped dosage of nZVI, the pre-doped agent (Al13@nZVI) showed 23% improvement of the maximum removal rate of Carbamazepine compared with Al13 under pH 7. It was found that Al13@nZVI could produce H2O2 in situ at pH 2 to pH 8, especially under acid conditions. By the analysis of FT-IR, it could be found that the groups of C-N, benzene, and CO were disappeared after treatment. Instead, -NO2 was found in treated water which indicated the breakage and oxidation of amine group. Thus, the effects of pH on Al13 and Al13@nZVI were different. Al13 will undergo depolymerization and decompose into small polymers with low positive charge density with the increasing of pH, while, because of Al13@nZVI having oxidation ability, effect of pH on Al13@nZVI was not that significant. The influence of Humic acid (HA) with different concentration on CBZ removal were analyzed. The system with 2 mg/L HA showed better removal performance of both CBZ and total dissolved organic carbon (DOC) compared to the system with 1 mg/L HA, which may because of the increase of the necessary nuclei for the flocs formation, as well as the bridging function by the long chain structure of HA. Moreover, Al13@nZVI was found improved the removal efficiency of organic matters with molecular weight about 1500–2000 Da compared to Al13.

Degradation of trichloroethylene by biochar supported nano zero-valent iron (BC-nZVI): The role of specific surface area and electrochemical properties

Direct electron transfer and the involvement of atomic hydrogen (H⁎) are considered the main mechanisms for reductive dechlorination promoted by nano zero-valent iron (nZVI) supported on highly conductive carbon. It is still unclear how precisely H⁎, the specific surface area, and the electrochemical characteristics contribute to biochar supported nano zero-valent iron (BC-nZVI) activity in chlorinated hydrocarbon contaminant removal. In this study, a range of BC-nZVIs were prepared by a liquid-phase reduction process, and the contributions of specific surface area and electrochemical performance to H⁎ generation and electron transfer have been assessed. The mechanism of trichloroethylene (TCE) dechlorination by BC-nZVIs has been evaluated in terms of removal efficiency and the ultimate degradation products. The results have demonstrated that BC-nZVIs exhibit a higher specific surface area and TCE degradation efficiency compared with the bare nZVI. Ethane, ethylene, and acetylene were the principal TCE degradation products. The elimination of TCE was not significantly affected by differences in BC-nZVI specific surface area, but electron transfer and sustained generation of H⁎ were dependent on the catalyst electrochemical characteristics. The electrochemical properties of biochar serve to lower the corrosion potential of nZVI, improving electronic transfer capability and reactivity and promoting direct electron transfer for the degradation of TCE. In addition, the enhanced electrochemical properties also facilitate the reaction of nZVI with water and can promote the sustained generation of H⁎. Generation of H⁎ played a key role in reductive dechlorination over BC-nZVIs, which was related to the properties of the biochar support. This study focuses on the role of H⁎ and electrochemical performance in TCE reductive dechlorination, and provides a theoretical foundation and experimental support for the practical application of BC-nZVIs.

Persulfate activation using leonardite char-supported nano zero-valent iron composites for styrene-contaminated soil and water remediation

Effective in-situ technology to treat carcinogenic compounds in contaminated areas poses a major challenge. Our objective was to load nano-zero-valent iron (nZVI) onto leonardite char (LNDC), an alternative carbon source from industrial waste, for use as a persulfate (PS) activator for styrene treatment in soil and water. By adding a surfactant during synthesis, cetyltrimethylammonium bromide (CTAB) promotes a flower-like morphology and the nZVI formation in smaller sizes. Results showed that nZVI plays a crucial role in PS activation in both homogeneous and heterogeneous reactions to generate reactive oxygen species (ROS), which can remove 98% of styrene within 20 min. Quenching experiments indicated that singlet oxygen (1O2), superoxide radicals (O2•–), and sulfate radicals (SO4•–) were the main species working together to degrade styrene. XPS analysis also revealed a role of surface oxygen-containing groups (i.e., CO, C–OH) in activating PS for SO4•– and 1O2 generation. The possible reaction mechanism of PS activation by LNDC-CTAB-nZVI composite and factors affecting treatment efficiency (i.e., PS concentration, catalyst dosage, pH, and humic acid) were illustrated. The molarity/molality ratio of PS to nZVI should be set greater than 1 for effective styrene removal. GC-MS analysis showed that styrene was degraded to a less toxic benzaldehyde intermediate. However, the excessive use of PS and catalysts can harm plant growth, requiring a combining approach to achieve safer use for real applications. Overall results supported the use of the LNDC-CTAB-nZVI/PS system as an efficient in-situ treatment technology for soil and water remediation.

Enhanced removal of estrogens from simulated wastewater by biochar supported nanoscale zero-valent iron: performance and mechanism

The intensification of estrogen non-point source pollution has drawn global attention due to their contribution to ecological environment problems worldwide, and it is critical to develop effective, economic and eco-friendly methods for reducing estrogens pollution. To address the agglomeration and oxidation of nano zero-valent iron (nZVI), biochar-nanoscale zero-valent iron composite (nZVI-biochar) could be a feasible choice for estrogens removal. This study summarized biochar and nZVI-biochar preparation, characterization, and unusual applications for estrone (E1), 17β-estradiol (E2), and estriol (E3) removal. The properties of biochar and nZVI-biochar in characterization, effects of influencing factors on the removal efficiency, adsorption kinetics, isotherm and thermodynamics were investigated. The experiment results showed that nZVI-biochar exhibited the superior removal performance for estrogens pollutants compared to biochar. Based on the quasi-second-order model, estrogens adsorption kinetics were observed, which supported the mechanism that chemical and physical adsorption existed simultaneously on estrogens removal. The adsorption isotherm of estrogens could be well presented by the Freundlich model and thermodynamics studies explained that nZVI-biochar could spontaneously remove estrogens pollutants and the main mechanisms involved π-π interaction, hydrophobic interaction, hydrogen bonding and degradation through ring rupture. The products analyzed by GC–MS showed that estrogens degradation was primarily attributed to the benzene ring broken, and Fe3+ promoted the production of free radicals, which further proved that nZVI-biochar had the excellent adsorption performances. Generally, nZVI-biochar could be employed as a potential material for removing estrogens from wastewater.Graphical

Microbial mechanism underlying the effect of biochar supported nano zero-valent iron on the anaerobic digestion of food waste

Anaerobic digestion (AD) is one of the effective methods to treat the food waste (FW). In this study, biochar supported nano zero-valent iron (BC-nZVI) was prepared by carbon thermal reduction process. The effects of concentrations (1, 2 and 3 g/L) of BC-nZVI on methane production, microorganisms and metabolic mechanism during the AD of food waste were investigated. The results showed that 1 g/L of BC-nZVI was the best concentration for methane production. The cumulative methane production was enhanced by 29.54% at BC-nZVI 1 g/L. Microbial community analysis showed that BC-nZVI mainly increased the abundances of hydrolytic bacteria (including Bacteroidetes_vadinHA17, Proteiniphilum, Syntrophobacter) and acetoclast (Methanosaeta). Further exploration of the mechanism using PICRUSt2 version based on 16 S rRNA gene sequence analysis indicated that the addition of BC-nZVI promoted the abundances of enzymes related to methane metabolism such as the phosphate acetyltransferase and the methyl-coenzyme M reductase alpha subunit, which made the AD system stable.

Relationship Between Sulfidated Nano Zero Valent Iron and a Reductive Dechlorinating Microbial Culture - Synergistic or Antagonistic?

Sulfidated nano zerovalent iron (S-nZVI) has garnered significant attention from researchers due to its potential for effective in-situ remediation applications. Compared to bare nZVI, sulfidation process enhances its reactivity towards chlorinated volatile organic compounds (cVOCs) and improves its longevity (Nunez Garcia et al. 2021). Stabilizing the particles with a polymer, like carboxymethyl cellulose (CMC), can further improve the performance of S-nZVI by imparting higher stability, less toxicity towards microbial cells, and a potential biostimulatory effect, making CMC-S-nZVI a promising in-situ remediation technology (Nunez Garcia et al. 2021). Recently, CMC-S-nZVI has also been applied for field-scale remediation (Nunez Garcia et al. 2020;Brumovský et al. 2021). The contaminated sites usually have multiple pollutants and not all can be degraded by CMC-S-nZVI, thus, leaving some recalcitrant cVOCs untreated (Zhang et al. 2021). Biodegradation of cVOCs by dechlorinating microbial cultures may generate highly toxic intermediates like vinyl chloride (Kocur et al. 2016). However, coupling the two treatments may be able to compensate for each other’s drawbacks, resulting in higher efficiency, longer effectiveness, non-accumulation of intermediates, and degradation of a wider range of target contaminants. However, interacting effects of CMC-S-nZVI on dechlorinating microbial cultures have not been studied yet. This research investigates the potential of combining CMC-S-nZVI and a reductive dechlorinating microbial culture (KB-1) to degrade trichloroethylene (TCE) and 1,2-dichloroethane (1,2-DCA). CMC-S-nZVI was synthesized by a two-step method: (1) CMC-nZVI was first synthesized by reducing ferrous sulfate-CMC solution with dropwise addition of sodium borohydride solution with continuous mixing and (2) then sodium dithionite solution was added as a sulfidation agent to the freshly-synthesized CMC-nZVI (Nunez Garcia et al. 2020). Effects of different sulfur-iron ratios (S/Fe), iron, and CMC concentrations on TCE degradation were studied to obtain an effective CMC-S-nZVI formulation. Results showed a successful TCE removal by the CMC-S-nZVI but 1,2-DCA was not degraded. TCE degradation by CMC-S-nZVI fitted the first-order kinetic model, with the highest degradation rate constant (0.35 h-1) achieved at S/Fe = 0.1 with iron and CMC concentrations of 1 gL-1 and 0.4 wt%, respectively. This CMC-S-nZVI formulation was further tested to examine its interaction with KB-1 in terms of cVOCs dechlorination and microbial population responses. A four-day aged CMC-S-nZVI was also tested to study the effect of aging. Degradation pathways for TCE and 1,2-DCA were proposed, based on the formation of degradation products. For the coupled treatment, an increase in microbial abundance was observed by quantifying DNA concentrations. This demonstrated a synergistic relationship between CMC-S-nZVI and KB-1. Unlike the CMC-S-nZVI only treatment, microcosms containing both CMC-S-nZVI and KB-1 were found to successfully degrade the 1,2-DCA. The coupled treatment degraded TCE and 1,2-DCA at faster rates and generated lesser amounts of vinyl chloride than the KB-1 only treatment, confirming the biostimulatory effect of CMC-S-nZVI. In the KB-1 only treatment with CMC as the sole carbon and energy source, TCE and 1,2-DCA were successfully dechlorinated. Transmission electron microscopy illustrated that CMC-S-nZVI particles were attached to the microbes but did not penetrate the bacterial cells. In summary, synergistic abiotic-biotic dechlorination of TCE and 1,2-DCA was achieved by the combined treatment of CMC-S-nZVI and KB-1, suggesting that multi-contaminant sites can benefit from this approach. Additionally, the four-day aged CMC-S-nZVI performed similar to the freshly-synthesized one, demonstrating that the field-scale remediation can have a more feasible time scale for the preparation and application of these amendments.

Cr(VI) removal from wastewater using nano zero-valent iron and chromium-reducing bacteria.

Significant global efforts are currently underway to alleviate the presence of toxic metals in water bodies, aiming to encourage a sustainable environment. Nevertheless, the scientific community has yet to methodically inspect the performance and mechanisms underlying the interaction between nanomaterials and microorganisms in this context. Therefore, this study seeks to address this knowledge gap by developing a novel system that integrates nano zero-valent iron (nZVI) with chromium-reducing bacteria (CrRB) to efficiently remove Cr(VI) from water sources. The combined use of RBC600 and CrRB resulted in a Cr(VI) removal rate of 77.73%, displaying a substantial improvement of 17.61% compared to the use of CrRB alone. The efficacy of Cr(VI) elimination was observed to be affected by several factors within the system, such as the pH value, the quantity of nZVI added, the degree of CrRB inoculation, and the initial concentration of Cr(VI) at the onset of the experiment. When the pH was adjusted to 5, the complete removal of 200 mg/L Cr(VI) was achieved within 36 h. Increasing the dosage of nZVI to above 2 g/L resulted in the complete elimination of Cr(VI) from the solution within 72 h. This can be attributed to the availability of more reaction sites for the reduction of Cr(VI), facilitated by the higher nZVI dose. Additionally, the increased dose of nZVI allowed for the dissolution of more reactive Fe(II) ions. The characterization analysis, high-throughput sequencing, and fluorescence quantitative PCR results have established that CrRB and its extracellular polymer effectively reduce and complex Cr(VI). This process facilitated the dissolution of the passivated layer on the surface of nZVI, thus significantly enhancing the efficiency of nZVI in responding to Cr(VI). Additionally, the presence of nZVI created a favorable living environment for CrRB, resulting in increased richness and diversity within the CrRB community. These findings provide valuable preliminary insights into the mechanism underlying Cr(VI) elimination by the synergistic interaction between nZVI and CrRB. Therefore, this study establishes a solid theoretical foundations for the application of nano-bio synergy in the remediation of Cr(VI).

Subsurface Transport of Sulfidated Nano Zero Valent Iron and In Situ Biogeochemical Transformation of Chlorinated Solvents: A Field Study

In situ chemical reduction of chlorinated volatile organic compounds (cVOCs) by nano zero-valent iron (nZVI) has been widely applied in the past 20 years, but with limited effectiveness for bare nZVI due to rapid particle settling, short lifespan, and low reactivity. Stabilization and sulfidation of nZVI have improved its mobility and longevity, increased reactivity towards cVOCs, and reduced toxicity to microbes (Nunez Garcia et al. 2021). In the first-ever CMC-S-nZVI field trial, nZVI sulfidated by dithionite (S-nZVI) and stabilized by carboxymethyl cellulose (CMC) was injected into the subsurface of a site contaminated with a wide range of cVOCs. Multi-level wells were installed to monitor the transport of the CMC-S-nZVI suspension and its remedial performance for two years. Short-term (0-17 days) monitoring demonstrated a good transport of the suspension in the down- and up-gradient wells, in terms of total iron, boron, and sulfides which were major constituents of CMC-S-nZVI. Changes in concentrations of parent compounds, intermediates, and ethene showed effective dechlorination of high-chlorinated VOCs such as tetrachloroethene (PCE) and carbon tetrachloride (Nunez Garcia et al. 2020a, Nunez Garcia et al. 2020b). Long-term (157-729 days) performance was evaluated through temporal analyses of microbial communities, total iron, boron, and cVOCs in groundwater samples. Microbial populations, including organohalide-respiring bacteria, increased by >1 order of magnitude; with Geobacter being the most abundant. This long-term enrichment can be attributed to the low toxicity of CMC-S-nZVI and biostimulation by CMC and perhaps Fe3+. Non-metric multidimensional scaling analysis was carried out on microbial data grouped by depth range and proximity to the injection well. At locations that clearly received CMC-S-nZVI, there was a significant shift in microbial communities that was sustained for the long term. Iron concentrations increased substantially in long-term samples while boron concentrations decreased, suggesting that this iron did not come from CMC-S-nZVI. Microbial dissolution of iron minerals might have contributed to the increased iron content (Jones et al. 2006). Excess dithionite in CMC-S-nZVI would also have reductively dissolved native iron from the soil, as successfully demonstrated in the in situ redox manipulation (ISRM) technology wherein subsurface Fe3+ in soil was reduced to Fe2+ for long-term remedial purposes (Vermeul et al. 2000). Long-term changes in concentrations of lesser-chlorinated VOCs and hydrocarbons suggest that PCE was degraded via both the microbially-mediated sequential hydrogenolysis as well as the abiotic β-elimination. The intermediate vinyl chloride (VC) surprisingly did not accumulate in the current study, in contrast to the significant VC accumulation in a previous un-sulfidated CMC-nZVI trial at the same location (Kocur et al. 2016). Excess dithionite injected in this study might have avoided VC accumulation, as previously reported for ISRM treatment of a cVOCs-contaminated site (Vermeul et al. 2000). Additionally, the identified bacterial populations might have utilized sulfur species (from dithionite decomposition) and iron to form iron sulfides, which could dechlorinate cVOCs via in situ biogeochemical transformation (Kennedy et al. 2006). In summary, this study has demonstrated the long-term efficiency of CMC-S-nZVI for cVOCs removal through a combination of abiotic, biotic, and biostimulatory processes in the subsurface.

Immobilizing arsenic in contaminated anoxic aquifer sediment using sulfidated and uncoated zero-valent iron (ZVI)

Arsenic (As) is carcinogenic and of major concern in groundwater. We collected sediment material from a contaminated anoxic aquifer in Sweden and investigated the immobilization of As by four commercial zero-valent iron (ZVI) particles. Solid-phase As and Fe speciation was assessed using X-ray absorption spectroscopy (XAS) and solution-phase As speciation using chromatographic separation. Without ZVI addition, arsenite dominated in solution and As(V) species in the solid phase. Adding ZVI caused a sharp increase in solution pH (9.3–9.8), favoring As oxidation despite a lowered redox potential. ZVI greatly improved As retention by complex binding of arsenate to the Fe(III) (hydr)oxides formed by ZVI corrosion. Uncoated ZVI, both in nano- and microscale, performed better than their sulfidated counterparts, partly due to occlusion of As by the Fe(III) (hydr)oxides formed. The effect of particle size (micro vs. nano ZVI) on As immobilization was small, likely because immobilization was related to the corrosion products formed, rather than the initial size of the particles. Our results provide a strong geochemical background for the application of ZVI particles to remove As in contaminated aquifers under anoxic conditions and illustrate that immobilization mechanisms can differ between ZVI in As spiked solutions and sediment suspensions. Environmental implicationArsenic ranks first on the list by the US ATSDR of substances posing a threat to human health and the WHO considers groundwater the riskiest source for human intake of As. However, dealing with As contamination remains a scientific challenge. We studied the immobilization of groundwater As by commercially available ZVI particles at field-realistic conditions. Arsenic immobilization was highly efficient in most cases, and the results suggest this is a promising in situ strategy with long-term performance. Our results provide a strong geochemical background for using ZVI to remove As in contaminated anoxic aquifers.

Key role of La in La@nZVI/rGO for the efficient and steady PMS activation towards ofloxacin degradation via a non-radical process

The nano zero-valent iron (nZVI)/peroxymonosulfate (PMS)-based advanced oxidation processes (AOPs) are promising for removal of antibiotic contaminants in groundwater. However, the inherent defects of rapid passivation and inactivation limit the efficient and steady application of nZVI. Herein, the lanthanum@nZVI/rGO (La@nZVI/rGO) was synthesized in which nZVI was coated with La and distributed evenly on reduced graphene oxide (rGO) matrix. The introduction of La coating protected the nZVI from direct contact with PMS molecules thus the La@nZVI/rGO appeared efficient and steady activization of PMS to degrade ofloxacin (OFX) without rapid inactivation. The removal rate was promoted to 96.5 % compared with the uncoated nZVI/rGO (only 85.2 %). The degradation reaction represented steady and continuous activation of PMS with pseudo-first-order kinetics (0.0451 min−1). While the two-stage kinetics of nZVI/rGO/PMS with initial 0.2581 min−1 and instant 0.0024 min−1 resulted from the rapid inactivation of nZVI. The reaction of La@nZVI/rGO/PMS exhibited minimal leaching of Fe ions (less than 1.8 µg/L) while it reached 6.4 mg/L in nZVI/rGO/PMS. XRD and XPS analyses further demonstrated the excellent durability of La@nZVI/rGO and the obvious passivation of nZVI/rGO. ESR and quenching tests confirmed that La coating regulated the PMS activation and ROS generation mechanism. The degradation was dominated by 1O2-induced non-free radical process in La@nZVI/rGO/PMS system and different from radical oxidation in nZVI/rGO/PMS. Moreover, the dissolved oxygen and XPS analysis revealed the important role of La coating and oxygen vacancy in the catalytic degradation. This work could provide a novel understanding of the nZVI with protective coating in AOPs environmental remediation.

Sulfide-modified nanozerovalent iron for rapid decontamination of Cu(Ⅱ) complexes in high-salinity wastewater

Heavy metal complexes receive less attention, but they are more difficult to remove than the free heavy metals. Moreover, the high-salinity wastewaters from various industries hinder the removal of heavy metal complexes. Removal of the metal complexes is a top priority but a challenging task. Herein, a new strategy for removing Cu-EDTA from high-salinity wastewater with sulfide-modified nanozerovalent iron (S-NZVI) was proposed. The S-NZVI exhibited a considerable adsorption capacity for Cu-EDTA (∼83 mg Cu/g) at a high salt concentration (25 g/L NaCl). Similarly, the S-NZVI maintained excellent adsorption performance (∼83 mg Cu/g) in the presence of CaCl2, MgCl2, Na2SO4, and NaNO3 (25 g/L). The S-NZVI showed extremely high efficiency for Cu-EDTA removal; 50 mg/L of Cu-EDTA was almost completely removed in 1 min, and the kobs was approximately 1.5 g/(mg min). The S-NZVI showed an extensive pH working range, and within the pH range of 2–9, the Cu-EDTA was removed completely within 5 min. The excellent removal performance of the S-NZVI was due to the high reactivity and high affinity of NZVI for Cu, as well as the special substitution of Fe2+ and the interfacial reactions between S-NZVI and the copper complexes. Compared with other studies of Cu complex removal, removal with S-NZVI was a simpler process with higher efficiency. In brief, S-NZVI efficiently removed Cu complexes from harsh water environments and was reused many times. The process was simple and efficient and has broad application prospects.

Therapeutic and antioxidant potential of bionanofactory Ochrobactrum sp.-mediated magnetite and zerovalent iron nanoparticles against acute experimental toxoplasmosis.

The control of toxoplasmosis, a rampant one health disease, has been focussed on conventional antitoxoplasmic agents with their adverse outcomes, including serious side effects, treatment failure and emergence of drug resistant strains. Nanobiotechnology may provide a strong impetus for versatile alternative therapies against toxoplasmosis. Bionanofactory Ochrobactrum sp. strain CNE2 was recruited for the biosynthesis of functionalized magnetite iron nanoparticles (MNPs) and nanozerovalent iron (nZVI) under aerobic and anaerobic conditions and their therapeutic efficacy was evaluated against acute toxoplasmosis in murine model. The formation of self-functionalized spherical nanoparticles varied in size, identity and surface properties were substantiated. Mice were orally administered 20 mg/kg of each formulation on the initial day of infection and continued for seven consecutive days post infection (PI). Parasitological, ultrastructural, immunological, and biochemical studies were performed for assessment of therapeutic activity of biogenic iron nanoparticles (INPs). Parasitologically, MNPs showed the highest antitoxoplasmic efficacy in terms of 96.82% and 91.87% reduction in mean tachyzoite count in peritoneal fluid and liver impression smears, respectively. Lesser percentage reductions were recorded in nZVI-treated infected subgroup (75.44% and 69.04%). In addition, scanning electron microscopy (SEM) examination revealed remarkable reduction in size and extensive damage to the surface of MNPs-treated tachyzoites. MNPs-treated infected mice revealed a statistically significant increase in the serum levels of both interferon gamma (IFN-γ) to 346.2 ± 4.6 pg/ml and reduced glutathione (GSH) to 8.83 ± 0.30 mg/dl that subsequently exerted malondialdehyde (MDA) quenching action. MNPs showed a superior promising antitoxoplasmic activity with respect to both spiramycin (SPI) and nZVI. To best of our knowledge, this is the first study of a bio-safe oral iron nanotherapeutic agent fabricated via an eco-friendly approach that offers promising potential against acute experimental toxoplasmosis.

Enhanced retention of surface-adsorbed atomic hydrogen through sulfidation of nano zerovalent iron for water decontamination

Enhanced retention of surface-adsorbed atomic hydrogen through sulfidation of nano zerovalent iron for water decontamination