Eco-friendly nanoparticles: mechanisms and capacities for efficient removal of heavy metals and phosphate from water using definitive screening design approach.

Can nano-zero-valent iron, synthesized using oak leaf extract, be the key solution for water preservation, efficiently removing heavy metal ions and phosphate anions simultaneously? This research unveils how this technology not only promises high efficiency in the remediation of water resources, but also sets new standards for environmentally friendly processes. The high antioxidant capacity and high phenol content indicate suggest the possibility of oak-nZVI synthesis using oak leaf extract as a stable material with minimal agglomeration. The simultaneous removal of Cd and phosphates, as well as and Ni and phosphates was optimized by a statistically designed experiment with a definitive screening design approach. By defining the key factors with the most significant impact, a more efficient and faster method is achieved, improving the economic sustainability of the research by minimizing the number of experiments while maximizing precision. In terms of significance, four input parameters affecting process productivity were monitored: initial metal concentration (1-9 mg L-1), initial ion concentration (1-9 mg L-1), pH value (2-10), and oak-nZVI dosage (2-16 mL). The process optimization resulted in the highest simultaneous removal efficiency of 98.99 and 87.30% for cadmium and phosphate ions, respectively. The highest efficiency for the simultaneous removal of nickel and phosphate ions was 93.44 and 96.75%, respectively. The optimization process fits within the confidence intervals, which confirms the assumption that the selected regression model well describes the process. In the context of e of the challenges and problems of environmental protection, this work has shown considerable potential and successful application for the simultaneous removal of Cd(II) and Ni(II) in the presence of phosphates from water.

Enhanced uranium removal from aqueous solution by core-shell Fe0@Fe3O4: Insight into the synergistic effect of Fe0 and Fe3O4.

In this study, Fe0@Fe3O4 was synthesized and used to remove U(VI) from groundwater. Different experimental conditions and cycling experiments were used to investigate the performance of Fe0@Fe3O4 in the U(VI) removal, and the XRD, TEM, XPS and XANES techniques were employed to characterize the Fe0@Fe3O4. The results showed that the U(VI) removal efficiency of Fe0@Fe3O4 was 48.5 mg/g that was higher than the sum of removal efficiency of Fe0 and Fe3O4. The uranium on the surface of Fe0@Fe3O4 mainly existed as U(IV), followed by U(VI) and U(V). The Fe0 content decreased after reaction, while the Fe3O4 content increased. Based on the results of experiments and characterization, the enhanced removal efficiency of Fe0@Fe3O4 was attributed to the synergistic effect of Fe0 and Fe3O4 in which Fe3O4 accelerated the Fe0 corrosion that promoted the progressively formation of Fe(II) that promoted the reduction of adsorbed U(VI) to U(IV) and incorporated U(VI) to U(V). The performance of Fe0@Fe3O4 at near-neutrality condition was better than at acidic and alkalic conditions. The chloride ions, sulfate ions and nitrate ions showed minor effect on the Fe0@Fe3O4 performance, while carbonate ions exhibited significant inhibition. The metal cations showed different effect on the Fe0@Fe3O4 performance. The removal efficiency of Fe0@Fe3O4 decreased with the number of cycling experiment. Ionizing radiation could regenerate the used Fe0@Fe3O4. This study provides insight into the U(VI) removal by Fe0@Fe3O4 in aqueous solution.

Insight into the potentiality of nano zero-valent iron on enhancing the nitrite accumulation and phosphorus removal performance of endogenous partial denitrification systems.

Endogenous partial denitrification (EPD) has drawn a lot of interest due to its abundant nitrite (NO2--N) accumulation capacity. However, the poor phosphate (PO43--P) removal rate of EPD restricts its promotion and application. In this study, the potentiality of various nano zero-valent iron (nZVI) concentrations (0, 20, 40, and 80 mg/L) on NO2--N accumulation and PO43--P removal in EPD systems had been investigated. Results showed that nZVI improved NO2--N accumulation and PO43--P removal, with the greatest nitrate-to-nitrite transformation ratio (NTR) and PO43--P removal rate of 97.74 % and 64.76 % respectively at the optimum nZVI level (80 mg/L). Microbial community analysis also proved that nZVI had a remarkable influence on the microbial community of EPD. Candidatus_Competibacter was contribute to NO2--N accumulation which was enriched from 24.74 % to 40.02 %. The enrichment of Thauera, Rhodobacteraceae, Pseudomonas were contributed to PO43--P removal. The chemistry of nZVI not only compensated for the deficiency of biological PO43--P removal, but also enhanced NO2--N enrichment. Therefore, nZVI had the huge potentiality to improve the operational performance of the EPD system.

Transport of nZVI/copper synthesized by green tea extract in Cr(IV)-contaminated soil: modeling study and reduced toxicity.

In this study, nano-zero-valent iron/copper was synthesized by green tea extracts (GT-nZVI/Cu) and produced a stable suspension than nano-zero-valent iron synthesized by green tea extracts (GT-nZVI) injected into Cr(VI)-containing soil column. The equilibrium 1D-CDE model was successfully used to fit the penetration curves of Fe(tot), Fe(aq), and Fe(0) in order to determine the relevant parameters. The hydrodynamic dispersion coefficient of chromium-contaminated soil was 0.401 cm2·h-1, and the pore flow rate was 0.144 cm·h-1. The stable C/C0 of Fe(tot), Fe(aq), and Fe(0) in the effluent were retarded to 0.39, 0.79, and 0.11, respectively, compared to a ratio of 1 for the concentration of the tracer Cl- in the effluent to the concentration in the influent. Additionally, the 1D-CDE model describes the migration behavior of Cr(VI) with a high R2 (> 0.97). The obtained blocking coefficients declined gradually with increasing concentration of GT-nZVI/Cu suspension and decreasing concentration of Cr(VI). The content of reduced chromium in the soil decreased from 2.986 to 1.121 after remediation, while the content of more stable oxidizable chromium and residual chromium increased from 2.975 and 20.021 to 16.471 and 27.612. The phytotoxicity test showed that mung bean seeds still had a germination rate of 90% (control of 100%), root length of 29.63 mm (control of 35.25 mm), and stem length of 17.9 cm (control of 18.96 cm) after remediation with GT-nZVI/Cu. These indicated that GT-nZVI/Cu was effective in immobilizing Cr(VI) in the soil column and reduced the ecological threat. This study provides an analytical basis and theoretical model for the migration of chromium-contaminated soil in practical application.

Effect and mechanism of norfloxacin removal by Eucalyptus leaf extract enhanced the ZVI/H2O2 process.

The conventional ZVI/H2O2 technology suffers from poor reagent utilization, excess iron sludge generation, and strong low pH dependence. Therefore, eucalyptus leaf extract (ELE) was introduced to improve ZVI/H2O2 technology, and the efficacy and mechanism of ELE promoting ZVI/H2O2 technology were deeply explored. The results showed that the norfloxacin (NOR) removal and kobs of the ZVI/H2O2/ELE process were enhanced by 35.64 % and 3.27 times, respectively, compared to the ZVI/H2O2 process. In the ZVI/H2O2 process, the production of three reactive oxygen species (ROS: 1O2，·O2-，·OH) was effectively promoted by ELE so that the reaction efficacy was significantly enhanced. Moreover, the attack and degradation of pollutants by ROS was the main way to remove pollutants. With the introduction of ELE, the reactive sites on the catalyst appearance were increased to some extent, and the Fe(III)/Fe(II) cycle was improved. The analysis showed that ELE is rich in titratable acids and the ZVI/H2O2 technology is promoted mainly by lowering the pH of the process. In addition, the chelation of ELE and the reduction in pH by the ELE synergistically enhanced the ZVI/H2O2 technology, which significantly improved the reagent utilization (4.70 times for ZVI and 3.03 times for H2O2), broadened the pH range of the technology (6-9) and was able to effectively reduce the iron sludge contamination (30.33 %) of the process. Therefore, the study offers an important value to study eucalyptus leaves in micron-scale ZVI-Fenton technology.

Effect mechanism of micron-scale zero-valent iron enhanced pyrite-driven denitrification biofilter for nitrogen and phosphorus removal.

This study aims to explore the effect mechanism of micron-scale zero-valent iron (mZVI) to improve nitrogen and phosphorus removal in a pyrite (FeS2)-driven denitrification biofilter (DNBF) for the secondary effluent treatment. Two similar DNBFs (DNBF-A with FeS2 as fillers and DNBF-B with the mixture mZVI and FeS2 as carrier) were developed. The results showed that NO3--N, total nitrogen (TN) and PO43--P removal efficiencies were up to 91.64%, 67.44% and 80.26% in DNBF-B, which were obviously higher than those of DNBF-A (with NO3--N, TN and PO43--P removal efficiencies of 38.39%, 44.89% and 53.02%, respectively). Kinetic analysis of both PO43--P and NO3--N showed an increase in the rate constant (K) for DNBF-B compared to DNBF-A. The addition of mZVI not only improved the electron transport system activity (ETSA), but also achieved system Fe(II)/Fe(III) redox cycle in DNBF-B. In addition, the high-throughput sequencing analysis indicated that the addition of mZVI could obviously stimulate the enrichment of functional bacteria, such as Thiobacillus (11.99%), Mesotoga (7.50%), JGI-0000079D21 (6.37%), norank_f__Bacteroidetes_vadinHA17 (6.19%), Aquimonas (5.93%) and Arenimonas (3.97%). These genus played the important role in nitrogen and phosphorus removal in DNBF-B. Addition mZVI in the FeS2-driven denitrification biofilter is highly promising for TN and TP removal during secondary effluent treatment.

Coupling electrokinetic remediation with flushing using green tea synthesized nano zero-valent iron/nickel to remediate Cr (VI).

This study focuses on a flushing-electrokinetic remediation technology of hexavalent chromium from the chromium slag dump site. A suspension of nanoscale zero-valent iron/nickel fabricated from green tea (GT-nZVI/Ni), was employed as an eluent to degrade Cr (VI) and enhance the remediation effectiveness of a single EK. The removal efficiency of Cr (VI) was compared under different voltages, electrode spacings and pH values of the anolyte. The results demonstrated that the combined flushing and EK achieved a removal rate of Cr (VI) in the soil throughout all the experiments ranging from 83.08 to 96.97% after 120 h. The optimal result was obtained when the voltage was 28 V, the pH value of anolyte was 3 and the electrode spacing was 15 cm. The removal of Cr (VI) reached 91.49% and the energy consumption was 0.32606 kW·h·g-1. The underlying mechanisms responsible for the removal of Cr (VI) by GT-nZVI/Ni flushing-EK primarily involved electromigration, reduction and adsorption co-precipitation processes. The fractionation analysis of Cr (VI) concentration in the soil after remediation showed that the presence of GT-nZVI/Ni facilitated the conversion of Cr (VI) into oxidizable and residual states with low mobility and toxicity. The results of toxicity characteristic leaching procedure (TCLP) indicated that the leaching concentration of Cr (VI) was below 1 mg·L-1, complying with the standards set by the Environmental Protection Agency. Additionally, the phytotoxicity testing revealed that the germination index (GI) of the remediated soil reached 54.75%, indicating no potential harm to plants.

Immobilization of zinc and cadmium by biochar-based sulfidated nanoscale zero-valent iron in a co-contaminated soil: Performance, mechanism, and microbial response.

Mining and smelting of mineral resources causes excessive accumulation of potentially toxic metals (PTMs) in surrounding soils. Here, biochar-based sulfidated nanoscale zero-valent iron (SNZVI/BC) was designed via a one-step liquid phase reduction method to immobilize cadmium (Cd) and zinc (Zn) in a copolluted arable soil. A 60 d soil incubation experiment revealed that Cd and Zn immobilization efficiency by 6 % SNZVI/BC (25.2-26.2 %) was higher than those by individual SNZVI (13.9-18.0 %) or biochar (14.0-19.3 %) based on the changes in diethylene triamine pentaacetic acid (DTPA)-extractable PTM concentrations in soils, exhibiting a synergistic effect. Cd2+ or Zn2+ replaced isomorphously Fe2+ in amorphous ferrous sulfide, as revealed by XRD, XPS, and high-resolution TEM-EDS, forming metal sulfide precipitates and thus immobilizing PTMs. PTM immobilization was further enhanced by adsorption by biochar and oxidation products (Fe2O3 and Fe3O4) of SNZVI via precipitation and surface complexation. SNZVI/BC also increased the concentration of dissolved organic carbon and soil pH, thus stimulating the abundances of beneficial bacteria, i.e., Bacilli, Clostridia, and Desulfuromonadia. These functional bacteria further facilitated microbial Fe(III) reduction, production of ammonium and available potassium, and immobilization of PTMs in soils. The predicted function of the soil microbial community was improved after supplementation with SNZVI/BC. Overall, SNZVI/BC could be a promising functional material that not only immobilized PTMs but also enhanced available nutrients in cocontaminated soils.

The removal of antibiotic resistant bacteria and antibiotic resistance genes by sulfidated nanoscale zero-valent iron activating periodate: Efficacy and mechanism.

Antibiotic resistant bacteria (ARB) and antibiotic resistance genes (ARGs) have drawn much more attention due to their high risk on human health and ecosystem. In this study, the performance of sulfidated nanoscale zero-valent iron (S-nZVI)/periodate (PI) system toward ARB inactivation and ARGs removal was systematically investigated. The S-nZVI/PI system could realize the complete inactivation of 1 × 108 CFU/mL kanamycin, ampicillin, and tetracycline-resistant E. coli HB101 within 40 min, meanwhile, possessed the ability to remove the intracellular ARGs (iARGs) (including aphA, tetA, and tnpA) carried by E. coli HB101. Specifically, the removal of aphA, tetA, and tnpA by S-nZVI/PI system after 40 min reaction was 0.31, 0.47, and 0.39 log10copies/mL, respectively. The reactive species attributed to the E. coli HB101 inactivation were HO• and O2•-, which could cause the destruction of E. coli HB101 morphology and enzyme system (such as superoxide dismutase and catalase), the loss of intracellular substances, and the damage of iARGs. Moreover, the influence of the dosage of PI and S-nZVI, the initial concentration of E. coli HB101, as well as the co-existing substance (such as HCO3-, NO3-, and humic acid (HA)) on the inactivation of E. coli HB101 and its corresponding iARGs removal was also conducted. It was found that the high dosage of PI and S-nZVI and the low concentration of E. coli HB101 could enhance the disinfection performance of S-nZVI/PI system. The presence of HCO3-, NO3-, and HA in S-nZVI/PI system showed inhibiting role on the inactivation of E. coli HB101 and its corresponding iARGs removal. Overall, this study demonstrates the superiority of S-nZVI/PI system toward ARB inactivation and ARGs removal.

Improved electrochemical properties of graphite electrodes incubated with iron powders in rice-paddy fields boost power outputs from microbial fuel cells.

Studies have shown that the supplementation of anode-surrounding soil with zero-valent iron (ZVI) boosts power outputs from rice paddy-field microbial fuel cells (RP-MFCs). In order to understand mechanisms by which ZVI boosts outputs from RP-MFCs, the present study operated RP-MFCs with and without ZVI, and compositions of anode-associated bacteria and electrochemical properties of graphite anodes were analyzed after 3-month operation. Metabarcoding using 16S rRNA gene fragments showed that bacterial compositions did not largely differ among these RP-MFCs. Cyclic voltammetry showed improved electrochemical properties of anodes recovered from ZVI-supplemented RP-MFCs, and this was attributed to the adhesion of iron-oxide films onto graphite surfaces. Bioelectrochemical devices equipped with graphite anodes recovered from ZVI-supplemented RP-MFCs generated higher currents than those with fresh graphite anodes. These results suggest that ZVI is oxidized to iron oxides in paddy-field soil and adheres onto graphite anodes, resulting in the boost of power outputs from RP-MFCs.

Priming effects of nZVI on carbon sequestration and iron uptake are positively mediated by AM fungus in semiarid agricultural soils.

We investigated the priming effect of nanoscale zero-valent iron (nZVI) on carbon sink and iron uptake, and the possible mediation by AMF (arbuscular mycorrhizal fungi, Funneliformis mosseae) in semiarid agricultural soils. Maize seed dressings comprised of three nZVI concentrations of 0, 1, 2 g·kg-1 and was tested with and without AMF inoculation under high and low soil moistures, respectively. The ICP-OES observations indicated that both low dose of nZVI (1 g·kg-1) and high dose of nZVI (2 g·kg-1) significantly increased the iron concentrations in roots (L: 54.5-109.8 %; H: 119.1-245.4 %) and shoots (L: 40.8-78.9 %; H: 81.1-99.4 %). Importantly, the absorption and translocation rate of iron were substantially improved by AMF inoculation under the low-dose nZVI. Yet, the excess nanoparticles as a stress were efficiently relieved by rhizosphere hyphae, and the iron concentration in leaves and stems can maintain as high as about 300 mg·kg-1 while the iron translocation efficiency was reduced. Moreover, next-generation sequencing confirmed that appropriate amount of nZVI clearly improved the rhizosphere colonization of Funneliformis mosseae (p < 0.001) and the development of soil fungal community. Soil observations further showed that the hyphae development and GRSP (glomalin-related soil protein) secretion were significantly promoted (p < 0.05), with the increased R0.25 (< 0.25 mm) by 35.97-41.16 %. As a return, AMF and host plant turned to input more organic matter into soils for microbial growth and Fe uptake, and such interactions became more pronounced under drought stress. In contrast, high dose of nZVI (2 g·kg-1) tended to agglomerate on the surface of hyphae and spores, causing severe deformation and inactivation of AMF symbionts. Therefore, the priming effects of nZVI on carbon sequestration and Fe uptake in agricultural soils were positively mediated by AMF via the feedback loop of the plant-soil-microbe system for enhanced adaptation to global climate change.

Biosynthesis and Mathematical Interpretation of Zero-Valent Iron NPs Using Nigella sativa Seed Tincture for Indemnification of Carcinogenic Metals Present in Industrial Effluents.

Zero-valent iron nanoparticles (ZVI-NPs) are utilized for the indemnification of a wide range of environmental pollutants. Among the pollutants, heavy metal contamination is the major environmental concern due to their increasing prevalence and durability. In this study, heavy metal remediation capabilities are determined by the green synthesis of ZVI-NPs using aqueous seed extract of Nigella sativa which is a convenient, environmentally friendly, efficient, and cost-effective technique. The seed extract of Nigella sativa was utilized as a capping and reducing agent for the generation of ZVI-NPs. UV-visible spectrophotometry (UV-vis), scanning electron microscopy coupled with energy-dispersive X-ray spectroscopy (SEM-EDX), and Fourier transform infrared spectroscopy (FTIR) was used to investigate the ZVI-NP composition, shape, elemental constitution, and perspective functional groups, respectively. The biosynthesized ZVI-NPs displayed a peak of plasmon resonance spectra at 340 nm. The synthesized NPs were cylindrical in shape, with a size of 2 nm and (-OH) hydroxyl, (C-H) alkanes and alkynes N-C, N=C, C-O, =CH functional groups attached to the surface of ZVI-NPs. Heavy metals were successfully remediated from industrial wastewater collected from the various tanneries of Kasur. During the reaction duration of 24 h, different concentrations of ZVI-NPs (10 µg, 20 µg and 30 µg) per 100 mL were utilized for the removal of heavy metals from industrial wastewater. The 30 µg/100 mL of ZVI-NPs proved the pre-eminent concentration of NPs as it removed >90% of heavy metals. The synthesized ZVI-NPs were analyzed for compatibility with the biological system resulting in 87.7% free radical scavenging, 96.16% inhibition of protein denaturation, 60.29% and 46.13% anti-cancerism against U87-MG and HEK 293 cell lines, respectively. The physiochemical and exposure mathematical models of ZVI-NPs represented them as stable and ecofriendly NPs. It proved that biologically synthesized NPs from a seed tincture of Nigella sativa have a strong potential to indemnify heavy metals found in industrial effluent samples.

Effect and mechanism of norfloxacin removal by guava leaf extract in the ZVI/H2O2 system.

To overcome the bottlenecks of the conventional zero-valent iron Fenton-like (ZVI/H2O2) process, such as low reagent utilization, low applicable pH, and iron sludge contamination, guava leaf extract (GLE) was used as a green promoter to enhance ZVI/H2O2 process in this study. Compared with the ZVI/H2O2 system, the removal rate and kobs of norfloxacin by the ZVI/H2O2/GLE system were increased by 33.76% and 2.19 times, respectively. The experimental investigation of the mechanism showed that the attack of reactive oxygen species was the main pathway for the removal of pollutants, and three types of reactive oxygen species (1O2, O2-,·OH) generations in the ZVI/H2O2/GLE system were effectively promoted by the introduction of GLE. The reactivity improvement was mainly due to the decrease of pH. At the same time, the chelation of iron ions by GLE promoted the Fe(III)/Fe(II) cycle on the catalyst surface was also a minor mechanism to improve the reactivity. This study provides a crucial reference for the practical application of guava leaf to promote the ZVI/H2O2 process in environmental pollution control.

Enhanced anaerobic digestion performance of food waste by zero-valent iron and iron oxides nanoparticles: Comparative analyses of microbial community and metabolism.

The effects of zero-valent iron (ZVI) and iron oxides nanoparticles on anaerobic digestion (AD) performance of food waste (FW) were comparably clarified in this study. Results indicated that the nanoparticles supplement effectively enhanced the methane yields. As observed, these nanoparticles accelerated organics transformation and alleviated acidification process. Also, the enriched total methanogens and functional bacteria (e.g., Proteiniphilum) were consistent with the promotion of oxidative phosphorylation, citrate cycle, coenzymes biosynthesis and the metabolisms of amino acid, carbohydrate, methane. Additionally, these nanoparticles stimulated electron transfer potential via enriching syntrophic genera (e.g., Geobacter, Syntrophomonas), primary acetate-dependent methanogens (Methanosaeta, Methanosarcina) and related functions (pilus assembly protein, ferredoxins). By comparison, ZVI nanoparticle presented the excellent performance on methanogenesis. This study provides comprehensive understanding of the methanogenesis facilitated by ZVI and iron oxides nanoparticles through the enhancement of key microbes and microbial metabolisms, while ZVI is an excellent option for promoting the methane production.

Highly efficient removal of Se(IV) using reduced graphene oxide-supported nanoscale zero-valent iron (nZVI/rGO): selenium removal mechanism.

Se(IV) removal using nanoscale zero-valent iron (nZVI) has been extensively studied. Still, the synergistic removal of Se(IV) by reduced graphene oxide-supported nanoscale zero-valent iron (nZVI/rGO) has not been reported. In this study, nZVI/rGO was successfully synthesized for Se(IV) removal from wastewater. The effects of different environmental conditions (load ratio, dosage, initial pH) on Se(IV) removal by nZVI/rGO were investigated. When the load ratio is 10%, the dosage is 0.3 g/L, the initial pH is 3, and the removal rate is 99%. The adsorption isotherm and kinetics accorded with the Langmuir isotherm and first-order kinetics models (R2 > 0.99). The fitted maximum adsorption capacity reached up to 173.53 mg/g. NZVI/rGo and Se(IV) is a spontaneous endothermic reaction (△G < 0, △H > 0) and is characterized by EDS, XRD, and XPS before and after the reaction, to further clarify the reaction mechanism. The XPS narrow spectrum analysis suggested that Se(IV) was reduced to elemental selenium (Se(0)), while the intermediate Fe(II) was oxidized to form hydroxide precipitation. Therefore, nZVI/rGO was favored for Se-contaminated wastewater remediation.

Design of cryogel based CNTs-anchored polyacrylonitrile honeycomb film with ultra-high S-NZVI incorporation for enhanced synergistic reduction of Cr(VI).

An ultra-high NZVI-loaded PAN film (S-CPN) with a unique 3D honeycomb structure was designed based on the cryogel method of green solvent-induced pores and confinement of the spatially free conformation of films by anchoring carbon nanotubes (CNTs), supplemented sulfidation for removing hexavalent chromium (Cr(VI)), and characterized by SEM, AFM, BET, XRD, XPS, and electrochemical corrosion. The doping amounts of the compounds for S-CPN synthesis were optimized to be 0.075 g CNTs, 0.25 g Na2S, and 0.3 M FeSO4. S-CPN possessed a 175.247 m2/g specific surface area, -0.365 V reduction potential, and 46.54 mg/g ultra-high NZVI-loading. S-CPN had the strong activity of Cr(VI) removal and tolerance to coexisting ions. The removal efficiency remained at 80 % after age for 30 days or 5 cycles. The pseudo-first-order kinetics and Langmuir model were more favorable to simulate the adsorption of Cr(VI) on S-CPN. The thermodynamics show that S-CPN removing Cr(VI) was a spontaneous exothermic reaction. The reasons for these excellent properties were that CNTs improve the film porosity and ultra-high NZVI-loading, and synergistic the FeSX layer to chelates-reduces Cr(VI). This was the first time that honeycomb film with 3D structure and potential applications in heavy metal removal was developed via an eco-friendly strategy.

In situ formation of Ca(OH)2 coating shell to extend the longevity of zero-valent iron biochar composite derived from Fe-rich sludge for aqueous phosphorus removal.

Despite being an effective and attractive functional strategy for aqueous phosphorus (P) removal, the use of zero valent iron (ZVI) biochar composites has been severely impeded by rapid self-erosion. We describe a new approach for extending the lifespan of Fe-rich sludge-derived ZVI biochar composites via CaCl2 modification. Preliminary results showed that composites obtained at 900 °C without modification (MBC900) and at 900 °C with 100 g Cl/kg addition (MBC900100) had the highest P removal efficiency. In subsequent batch experiments, MBC900100 exhibited more stable P adsorption capacities than MBC900 over a wide pH range (4-10) and at various dosages, which was enhanced by the presence of HCO3-. The theoretical maximum P adsorption capacities of MBC900 and MBC900100 were 227.14 and 224.15 mg g-1, respectively. Kinetic analysis indicated that chemisorption dominated the removal process. Continuous experimental data using the Yoon-Nelson model indicated that MBC900100 had a considerably longer half-penetration time. The primary mechanism of P removal by MBC900 was Fe/C micro-electrolysis. As the embedded CaO formed a dissolvable Ca(OH)2 shell in situ on the surface of MBC900100, the phosphate formed a precipitate with free Ca2+ before being removed via micro-electrolysis. Overall, CaCl2 modification successfully enhanced the longevity of the ZVI biochar composites.

Self-cleaning and regenerable nano zero-valent iron modified PCN-224 heterojunction for photo-enhanced radioactive waste reduction.

The expansion of large-scale nuclear power causes a substantial volume of radioactive wastewater containing uranium to be released into the environment. Because of uranium's toxicity and bioaccumulation, it is critical to develop the efficient and sustainable materials for selective removal of uranium (VI). Herein, a regenerable anti-biofouling nano zero-valent iron doped porphyrinic zirconium metal-organic framework (NZVI@PCN-224) heterojunction system was successfully fabricated. Due to the Schottky-junction effect at the NZVI/MOF interface, the NZVI nanomaterial immobilized on PCN-224 could improve interfacial electron transfer and separation efficiency, and enhance entire reduction of highly soluble U(VI) to less soluble U(IV), involving photocatalytic reduction and chemical reduction. Meanwhile, the photocatalytic effect also prompts the NZVI@PCN-224 to produce more biotoxic reactive oxygen species (ROS), resulting in high anti-microbial and anti-algae activities. Under dark conditions, NZVI@PCN-224 with a large specific surface area could provide sufficient oxo atoms as the uranium binding sites and show the highest uranium-adsorbing capability of 57.94 mg/g at pH 4.0. After eight adsorption-desorption cycles, NZVI@PCN-224 still retained a high uranium adsorption capacity of 47.98 mg/g and elimination efficiency (91.72%). This sorption/reduction/anti-biofouling synergistic strategy of combining chelation, chemical reduction and photocatalytic performance inspires new insights for highly efficient treatment of liquid radioactive waste.

Remedial trial of sequential anoxic/oxic chemico-biological treatment for decontamination of extreme hexachlorocyclohexane concentrations in polluted soil.

During production of γ-hexachlorocyclohexane (γ-HCH), thousands of tons of other isomers were synthesized as byproducts, and after dumping represent sources of contamination for the environment. Several microbes have the potential for aerobic and anaerobic degradation of HCHs, and zero-valent iron is an effective remediation agent for abiotic dechlorination of HCHs, whereas the combination of the processes has not yet been explored. In this study, a sequence of anoxic/oxic chemico-biological treatments for the degradation of HCHs in a real extremely contaminated soil (10-30 g/kg) was applied. Approximately 1500 kg of the soil was employed, and various combinations of reducing and oxygen-releasing chemicals were used for setting up the aerobic and anaerobic phases. The best results were obtained with mZVI/nZVI, grass cuttings, and oxygen-releasing compounds. In this case, 80 % removal of HCHs was achieved in 129 days, and 98 % degradation was achieved after 1106 days. The analysis of HCHs and their transformation products proved active degradation when slight accumulation of the transformation product during the anaerobic phase was followed by aerobic degradation. The results document that switching between aerobic and anaerobic phases, together with the addition of grass, also created suitable conditions for the biodegradation of HCHs and monochlorobenzene/benzene by microbes.

Long-term nitrogen and phosphorus removal, shifts of functional bacteria and fate of resistance genes in bioretention systems under sulfamethoxazole stress.

To understand the long-term performance of bioretention systems under sulfamethoxazole (SMX) stress, an unplanted bioretention system (BRS) and two modified BRSs with coconut-shell activated carbon (CAC) and CAC/zero-valent-iron (Fe0) granules (CAC-BRS and Fe/CAC-BRS) were established. Both CAC-BRS and Fe/CAC-BRS significantly outperformed BRS in removing total nitrogen (TN) (CAC-BRS: 82.48%; Fe/CAC-BRS: 78.08%; BRS: 47.51%), total phosphorous (TP) (CAC-BRS: 79.36%; Fe/CAC-BRS: 98.26%; BRS: 41.99%), and SMX (CAC-BRS: 99.74%, Fe/CAC-BRS: 99.80%; BRS: 23.05%) under the long-term SMX exposure (0.8 mg/L, 205 days). High-throughput sequencing revealed that the microbial community structures of the three BRSs shifted greatly in upper zones after SMX exposure. Key functional genera, dominantly Nitrospira, Rhodoplanes, Desulfomicrobium, Geobacter, were identified by combining the functional prediction by the FAPROTAX database with the dominant genera. The higher abundance of nitrogen functional genes (nirK, nirS and nosZ) in CAC-BRS and Fe/CAC-BRS might explain the more efficient TN removal in these two systems. Furthermore, the relative abundance of antibiotic-resistant genes (ARGs) sulI and sulII increased in all BRSs along with SMX exposure, suggesting the selection of bacteria containing sul genes. Substrates tended to become reservoirs of sul genes. Also, co-occurrence network analysis revealed distinct potential host genera of ARGs between upper and lower zones. Notably, Fe/CAC-BRS succeeded to reduce the effluent sul genes by 1-2 orders of magnitude, followed by CAC-BRS after 205-day exposure. This study demonstrated that substrate modification was crucial to maintain highly efficient nutrients and SMX removals, and ultimately extend the service life of BRSs in treating SMX wastewater.