Highly selective synthesis of surface FeIV=O with nanoscale zero-valent iron and chlorite for efficient oxygen transfer reactions.

High-valent iron-oxo species (FeIV=O) has been a long-sought-after oxygen transfer reagent in biological and catalytic chemistry but suffers from a giant challenge in its gentle and selective synthesis. Herein, we propose a new strategy to synthesize surface FeIV=O (≡FeIV=O) on nanoscale zero-valent iron (nZVI) using chlorite (ClO2-) as the oxidant, which possesses an impressive ≡FeIV=O selectivity of 99%. ≡FeIV=O can be energetically formed from the ferrous (FeII) sites on nZVI through heterolytic Cl-O bond dissociation of ClO2- via a synergistic effect between electron-donating surface ≡FeII and proximal electron-withdrawing H2O, where H2O serves as a hydrogen-bond donor to the terminal O atom of the adsorbed ClO2- thereby prompting the polarization and cleavage of Cl-O bond for the oxidation of ≡FeII toward the final formation of ≡FeIV=O. With methyl phenyl sulfoxide (PMS16O) as the probe molecule, the isotopic labeling experiment manifests an exclusive 18O transfer from Cl18O2- to PMS16O18O mediated by ≡FeIV=18O. We then showcase the versatility of ≡FeIV=O as the oxygen transfer reagent in activating the C-H bond of methane for methanol production and facilitating selective triphenylphosphine oxide synthesis with triphenylphosphine. We believe that this new ≡FeIV=O synthesis strategy possesses great potential to drive oxygen transfer for efficient high-value-added chemical synthesis.

How does the biochar-supported sulfidized nanoscale zero-valent iron affect the soil environment and microorganisms while remediating cadmium contaminated paddy soil?

In previous studies, iron-based nanomaterials, especially biochar (BC)-supported sulfidized nanoscale zero-valent iron (S-nZVI/BC), have been widely used for the remediation of soil contaminants. However, its potential risks to the soil ecological environment are still unknown. This study aims to explore the effects of 3% added S-nZVI/BC on soil environment and microorganisms during the remediation of Cd contaminated yellow-brown soil of paddy field. The results showed that after 49 d of incubation, S-nZVI/BC significantly reduced physiologically based extraction test (PBET) extractable Cd concentration (P < 0.05), and increased the immobilization efficiency of Cd by 16.51% and 17.43% compared with S-nZVI and nZVI/BC alone, respectively. Meanwhile, the application of S-nZVI/BC significantly increased soil urease and sucrase activities by 0.153 and 0.446 times, respectively (P < 0.05), improving the soil environmental quality and promoting the soil nitrogen cycle and carbon cycle. The results from the analysis of the 16S rRNA genes indicated that S-nZVI/BC treatment had a minimal effect on the bacterial community and did not appreciably alter the species of the original dominant bacterial phylum. Importantly, compared to other iron-based nanomaterials, incorporating S-nZVI/BC significantly increased the soil organic carbon (OC) content and decreased the excessive release of iron (P < 0.05). This study also found a significant negative correlation between OC content and Fe(II) content (P < 0.05). It might originate from the reducing effect of Fe-reducing bacteria, which consumed OC to promote the reduction of Fe(III). Accompanying this process, the redistribution of Cd and Fe mineral phases in the soil as well as the generation of secondary Fe(II) minerals facilitated Cd immobilization. Overall, S-nZVI/BC could effectively reduce the bioavailability of Cd, increase soil nutrients and enzyme activities, with less toxic impacts on the soil microorganisms.

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.

Investigate the multipath erasure of nitrobenzene over nanoscale zero-valent-iron/N-doped biochar hybrid with extraordinary reduction performance.

In this study, the facile carbothermal reduction method was enforced using urea as dopant to modify the structure and chemical composition of nanoscale zero-valent-iron/biochar hybrid thereby boosting its reduction performance. Through fine-tuning the N-doped amount, the optimal nZVI/N-doped BC was obtained, which exhibited more active sites (nZVI, persistent free radicals (PFRs), pyrrolic-N) and superior electrochemical conductivity. With these blessings, the electrons originating from galvanic cell reaction could zip along the highway within the hybrid. Taking nitrobenzene (NB) as the target pollutant, the quantitative analysis revealed that the NB reduction and adsorption removal efficiency were dramatically improved by 2.42 and 2.78 times, respectively. What's more, combining the in-situ experimental detection and theoretical calculations, unexpected NB reductive multipath with respect to PFRs and pyrrolic-N accelerating the Fe3+/Fe2+ cycle within the nZVI/N-doped BC system was decoded. The enhancement of Fe3+/Fe2+ cycle improved the electron utilization efficiency and maintained the reduction reactivity of the hybrid. This work raised awareness of the mechanisms regarding the reduction performance of nZVI/N-doped BC elevated by N-doped and the pollutant reductive pathway within the system, uncovered the dusty roles of PFRs and N-species during the reduction process.

Molybdenum disulfide co-catalysis boosting nanoscale zero-valent iron based Fenton-like process: Performance and mechanism.

The conventional Fenton process has the drawbacks of low efficiency of Fe3+/Fe2+ conversion, low utilization of H2O2, and narrow range of pH. In this paper, molybdenum sulfide (MoS2) was used as a co-catalyst to boost the nanoscale zero-valent iron (nZVI) based heterogeneous Fenton-like process for the degradation of Rhodamine B (RhB). The catalytic performance, influences of parameters, degradation mechanism, and toxicity of intermediates were explored. Compared with the conventional like-Fenton process, the existence of MoS2 accelerated the decomposition of H2O2 and the RhB degradation rate constant of MoS2/nZVI/H2O2 reached more than six times that of nZVI/H2O2. In addition, the effective pH range of MoS2/nZVI/H2O2 was broadened to 9.0 with 84.9% of RhB being removed within 15 min. The co-catalytic system of MoS2 and nZVI was stable and had high reusability according to the results of four consecutive runs. Quenching tests and electron paramagnetic resonance (EPR) demonstrated that hydroxyl radical (·OH), superoxide anions (·O2-), and singlet oxygen (1O2) were all involved in MoS2/nZVI/H2O2. Compared with nZVI/H2O2 system, MoS2 not only increased the corrosion of nZVI but also accelerated the conversion of Fe3+/Fe2+. ECOSAR analysis suggested that the overall acute and chronic toxicity of the degradation products decreased after treatment. Hence, this MoS2 co-catalytic nZVI based Fenton-like process can be used as a promising alternative for the treatment of organic wastewater.

Polycaprolactone-Modified Biochar Supported Nanoscale Zero-Valent Iron Coupling with Shewanella putrefaciens CN32 for 1,1,1-Trichloroethane Removal from Simulated Groundwater: Synthesis, Optimization, and Mechanism.

1,1,1-Trichloroethane (1,1,1-TCA) is a typical organochloride solvent in groundwater that poses threats to human health and the environment due to its carcinogenesis and bioaccumulation. In this study, a novel composite with nanoscale zero-valent iron (nZVI) supported by polycaprolac-tone (PCL)-modified biochar (nZVI@PBC) was synthesized via solution intercalation and liquid-phase reduction to address the 1,1,1-TCA pollution problem in groundwater. The synergy effect and improvement mechanism of 1,1,1-TCA removal from simulated groundwater in the presence of nZVI@PBC coupling with Shewanella putrefaciens CN32 were investigated. The results were as follows: (1) The composite surface was rough and porous, and PCL and nZVI were loaded uniformly onto the biochar surface as micro-particles and nanoparticles, respectively; (2) the optimal mass ratio of PCL, biochar, and nZVI was 1:7:2, and the optimal composite dosage was 1.0% (w/v); (3) under the optimal conditions, nZVI@PBC + CN32 exhibited excellent removal performance for 1,1,1-TCA, with a removal rate of 82.98% within 360 h, while the maximum removal rate was only 41.44% in the nZVI + CN32 treatment; (4) the abundance of CN32 and the concentration of adsorbed Fe(II) in the nZVI@PBC + CN32 treatment were significantly higher than that in control treatments, while the total organic carbon (TOC) concentration first increased and then decreased during the culture process; (5) the major improvement mechanisms include the nZVI-mediated chemical reductive dechlorination and the CN32-mediated microbial dissimilatory iron reduction. In conclusion, the nZVI@PBC composite coupling with CN32 can be a potential technique to apply for 1,1,1-TCA removal in groundwater.

Degradation behaviors and accumulative effects of coexisting chlorobenzene congeners on the dechlorination of hexachlorobenzene in soil by nanoscale zero-valent iron.

It is well known that many chlorinated organic pollutants can be dechlorinated by nanoscale zero-valent iron. However, in the real chlorinated organic compounds contaminated soil, the congeners of high- and low-chlorinated isomer often coexist and their dechlorination behaviors are poorly known, such as hexachlorobenzene (HCB). In this work, the degradation behaviors of three coexisting chlorobenzene congeners pentachlorobenzene (PeCB), 1,2,4,5-tetrachlorobenzene (1,2,4,5-TeCB) and 1,2,4-trichlorobenzene (1,2,4-TCB) and the influence of initial pH and reaction temperature on the dechlorination of HCB in HCB-contaminated soil by nanoscale zero-valent iron were studied. The amount and extent of accumulated coexisting chlorobenzenes was analyzed under different environmental conditions. The results indicate that nanoscale zero-valent iron can improve the degradation efficiency of highly toxic chlorinated benzenes and reduce the accumulative effects of highly toxic chlorinated benzenes on dechlorination of HCB. The accumulative effects of three coexisting chlorobenzene congeners on the dechlorination of HCB were ranked as follows: 1,2,4-TCB > 1,2,4,5-TeCB > PeCB.

Even Incorporation of Nitrogen into Fe0 Nanoparticles as Crystalline Fe4N for Efficient and Selective Trichloroethylene Degradation.

Surface modification of microscale Fe powder with nitrogen has emerged recently to improve the reactivity of Fe0 for dechlorination. However, it is unclear how an even incorporation of a crystalline iron nitride phase into Fe0 nanoparticles affects their physicochemical properties and performance, or if Fe0 nanoparticles with a varied nitridation degree will act differently. Here, we synthesized nitridated Fe0 nanoparticles with an even distribution of N via a sol-gel and pyrolysis method. Nitridation expanded the Fe0 lattice and provided the Fe4N species, making the materials more hydrophobic and accelerating the electron transfer, compared to un-nitridated Fe0. These properties well explain their reactivity and selectivity toward trichloroethylene (TCE). The TCE degradation rate by nitridated Fe0 (up to 4.8 × 10-2 L m-2 h-1) was much higher (up to 27-fold) than that by un-nitridated Fe0, depending on the nitridation degree. The materials maintained a high electron efficiency (87-95%) due to the greatly suppressed water reactivity (109-127 times lower than un-nitridated Fe0). Acetylene was accumulated as the major product of TCE dechlorination via ß-elimination. These findings suggest that the nitridation of Fe0 nanoparticles can change the materials' physicochemical properties, providing high reactivity and selectivity toward chlorinated contaminants for in situ groundwater remediation.

Synergistic Effect of Soil Organic Matter and Nanoscale Zero-Valent Iron on Biodechlorination.

Nanoscale zero-valent iron (nZVI) provides a promising solution for organochlorine (OC)-contaminated soil remediation. However, the interactions among nZVI, soil organic matter (SOM), and indigenous dechlorinating bacteria are intricate, which may result in unascertained effects on the reductive degradation of OCs and merits specific investigation. Herein, we isolated an indigenous dehalogenation bacterium (Burkholderia ambifaria strain L3) from a paddy soil and further investigated the biodechlorination of pentachlorophenol (PCP) with individual and a combination of SOM and nZVI. In comparison with individual-strain L3 treatment, the cotreatment with nZVI or SOM increased the removal efficiency of PCP from 34.4 to 44.3-54.2% after 15 day cultivation. More importantly, a synergistic effect of SOM and nZVI was observed on the PCP removal by strain L3, and the PCP removal efficiency reached up to 75.3-84.5%. Other than the biodegradation through ortho- and meta-substitution under the individual application of SOM or nZVI, PCP was further biodegraded to 2,4,6-trichlorophenol (TCP) through para-substitution by the isolated bacteria with the cotreatment of SOM and nZVI. The main roles of the nZVI-SOM cotreatment in the biodegradation included the SOM-facilitated microbial proliferation, the nZVI-promoted microbial transformation of SOM, and the induced higher electron transport capacity of redox Fe-PCP biocycling. These findings provide a novel insight into the action of nZVI in environmental remediations.

Insights into the mechanism underlying remediation of Cr(VI) contaminated aquifer using nanoscale zero-valent iron@reduced graphene oxide.

Currently, there is an urgent need to develop functional nanomaterials for highly effective environmental remediation. However, the long-term effect of remedial materials upon their injection into contaminated aquifer has frequently been overlooked. Here, the remediation of Cr(VI) contaminated aquifer by reduced graphene oxide (rGO) supported nanoscale zero-valent iron (nZVI@rGO) was investigated from a long-term perspective. The performances of nZVI@rGO samples with different rGO loadings in the removal of aqueous Cr(VI) were evaluated in batch experiments. The electron transfer properties different nZVI@rGO samples were investigated by measuring their corrosive potentials using the steady-state Tafel polarization curves. The results show that the electron transfer efficiency between Cr(VI) and nZVI@rGO is enhanced owing to the large reactive conjugated structure of rGO. Besides, the surface passivation of nZVI is effectively retarded due to the uniform accommodation of Cr(III) precipitates on rGO. The structure and composition of nZVI@rGO before and after Cr(VI) removal were analyzed by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The characterization results revealed that most Cr(VI) ions (∼90%) will be reduced to Cr(III) precipitates on nZVI@rGO as the passivation product. Accordingly, Cr(VI) ions tend to react more readily at less blocked regions on the surface of rGO, and a layer-by-layer passivation model on nZVI@rGO surface is proposed. Our results provide new insights into the mechanism underlying the long-term remediation of Cr(VI) contaminated aquifer using nZVI@rGO, which helps design new materials and approaches for practical in-situ remediation engineering.

Synergistic removal of As(III) and Cd(II) by sepiolite-modified nanoscale zero-valent iron and a related mechanistic study.

Arsenic (As) and cadmium (Cd) are two highly toxic elements. In recent years, many newly synthesized chemical materials have been used widely for treatments of As- and Cd-contaminated effluents. However, most materials do not exhibit high efficiencies for simultaneous removal of As and Cd from water systems. Our study established a simple scheme for synthesizing a sepiolite (SEP)-modified nanoscale zero-valent iron (S-nZVI) for simultaneous removal of coexisting As and Cd from water and illuminated a possible underlying mechanism. Batch experiments showed that the maximum capacities for adsorption of As(III) and Cd(II) by S-nZVI were 230.29 mg/g and 11.37 mg/g, respectively, which represented better effects than those of other materials, as reported previously. Removal of Cd(II) depended on pH, but As(III) removal showed little dependence on pH. Coexisting ions such as phosphate (PO43-) and the conjugate base of humic acid (HA) significantly inhibited simultaneous removal of As(III) and Cd(II). In the mixed As(III)-Cd(II) system, the presence of As(III)-pretreated S-nZVI significantly enhanced Cd(II) adsorption by a factor of four over that seen for aqueous solution without As(III). XRD and XPS results showed that CdFe2O4 (Fe-O-Cd), Fe2As2O14 or FeAsO4 (Fe-O-As) were formed after As(III) and Cd(II) were captured by S-nZVI. However, a further zeta (ζ) potential analysis showed that the mechanism for As(III) and Cd(II) adsorption by S-nZVI is not just simple formation of the above chemicals, since the adsorbed As(III) increased the negative charge of S-nZVI; this suggested an electrostatic attraction between S-nZVI and Cd(II) and indicated that adsorbed As(III) created new sorption sites for Cd(II), which enhanced Cd(II) sorption via formation of ternary complexes (Fe-As-Cd). These results suggested that S-nZVI is a promising material for in situ remediation of heavy metal-contaminated groundwaters or paddy soils.

Biochar-supported nZVI for the removal of Cr(VI) from soil and water: Advances in experimental research and engineering applications.

Over the past decade, biochar-supported nZVI composites (nZVI/biochar) have been developed and applied to treat various pollutants due to their excellent physical and chemical properties, especially in the field of chromium (VI) removal. This paper reviewed the factors influencing the preparation and experiments of nZVI/biochar composites, optimization methods, column experimental studies and the mechanism of Cr(VI) removal. The results showed that the difference in raw materials and preparation temperature led to the difference in functional groups and electron transfer capabilities of nZVI/biochar materials. In the experimental process, pH and test temperature can affect the surface chemical properties of materials and involve the electron transfer efficiency. Elemental doping and microbial coupling can effectively improve the performance of nZVI/biochar composites. In conclusion, biochar can stabilize nZVI and enhance electron transfer in nZVI/biochar materials, enabling the composite materials to remove Cr(VI) efficiently. The study of column experiments provides a theoretical basis for applying nZVI/biochar composites in engineering. Finally, the future work prospects of nZVI/biochar composites for heavy metal removal are introduced, and the main challenges and further research directions are proposed.

Sodium citrate and biochar synergistic improvement of nanoscale zero-valent iron composite for the removal of chromium (â ¥) in aqueous solutions.

Sodium citrate (SC) is a widely-used food and industrial additive with the properties of complexation and microbial degradation. In the present study, nano-zero-valent iron reaction system (SC-nZVI@BC) was successfully established by modifying nanoscale zero-valent iron (nZVI) with SC and biochar (BC), and was employed to remove Cr(Ⅵ) from aqueous solutions. The nZVI, SC-nZVI and SC-nZVI@BC were characterized and compared using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), thermogravimetric analyses (TGA), vibrating sample magnetometer (VSM), scanning electron microscope (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The results showed that nZVI was successfully loaded on the biochar, and both the agglomeration and surface passivation problems of nanoparticles were well resolved. The dosage of SC, C:Fe, initial pH and Cr(Ⅵ) concentration demonstrated direct effects on the removal efficiency. The maximum Cr(Ⅵ) removal rate and the removal capacity within 60 min were 99.7% and 199.46 mg/g, respectively (C:Fe was 1:1, SC dosage was 1.12 mol.%, temperature was 25°C, pH = 7, and the original concentration of Cr(Ⅵ) was 20 mg/L). The reaction confirmed to follow the pseudo-second-order reaction kinetics, and the order of the reaction rate constant k was as follows: SC-nZVI@BC > nZVI@BC > SC-nZVI > nZVI. In addition, the mechanism of Cr(Ⅵ) removal by SC-nZVI@BC mainly involved adsorption, reduction and co-precipitation, and the reduction of Cr(Ⅵ) to Cr(Ⅲ) by nano Fe0 played a vital role. Findings from the present study demonstrated that the SC-nZVI@BC exhibited excellent removal efficiency toward Cr(Ⅵ) with an improved synergistic characteristic by SC and BC.

Microbes team with nanoscale zero-valent iron: A robust route for degradation of recalcitrant pollutants.

Integrating nanoscale zero-valent iron (nZVI) with biological treatment processes holds the promise of inheriting significant advantages from both environmental nano- and bio-technologies. nZVI and microbes can perform in coalition in direct contact and act simultaneously, or be maintained in separate reactors and operated sequentially. Both modes can generate enhanced performance for wastewater treatment and environmental remediation. nZVI scavenges and eliminates toxic metals, and enhances biodegradability of some recalcitrant contaminants while bioprocesses serve to mineralize organic compounds and further remove impurities from wastewater. This has been demonstrated in a number of recent works that nZVI can substantially augment the performance of conventional biological treatment for wastewaters from textile and nonferrous metal industries. Our recent laboratory and field tests show that COD of the industrial effluents can be reduced to a record-low of 50 ppm. Recent literature on the theory and applications of the nZVI-bio system is highlighted in this mini review.

Remediation of hexavalent chromium in column by green synthesized nanoscale zero-valent iron/nickel: Factors, migration model and numerical simulation.

In this work, green tea extracts synthesized nanoscale zero-valent iron/nickel (GT-nZVI/Ni) was prepared and the Cr(VI) contaminated soil column was remediated by GT-nZVI/Ni suspension. The influence factors including the concentration, pH value and flow rate of GT-nZVI/Ni suspension were studied. Under the conditions of pH = 4, concentration of 0.15 g/L and flow rate of 1.25 mL/h, GT-nZVI/Ni suspension had the best reduction and immobilization effect on Cr(VI) in the soil column. Na+ and Ca2+ can promote the immobilization of Cr (VI) in soil, while humic acid weakened the immobilization of Cr (VI). After GT-nZVI/Ni is injected into the soil column, the content of weak acid extractable and reduced chromium is significantly reduced, and the toxic hazard of hexavalent chromium in the soil is greatly reduced. The 1D-CDE model was used to fit the breakthrough curves of Fe(tot), Fe(aq) and Fe(0), and the migration of GT-nZVI/Ni in Cr(VI) contaminated soil was simulated and predicted. Compared with the inert solute Cl-, the breakthrough curves of Fe (tot), Fe (aq) and Fe (0) in Cr (VI) contaminated soil column were significantly lagged, with delay coefficients of 2.465, 2.322 and 3.288, respectively. The reaction of GT-nZVI/Ni with Cr (VI) led to the decrease of Fe mobility. Finally, the outflow concentration of Fe (tot) was 0.064 g/L, and the loss was mainly due to reaction and retention in the soil. About 57.89% of GT-nZVI/Ni was retained in the soil.

Combined effect of nanoscale zero-valent iron and linear alkylbenzene sulfonate (LAS) to the freshwater algae Scenedesmus obliquus.

With wide use of nanoparticles, co-exposure of aquatic organisms to nanoparticles and organic pollutants often takes place in the environment. However, the combined effects are still rarely understood. In this study, in order to study the interaction and biological effects of nanoscale zero-valent iron (nZVI) and linear alkylbenzene sulfonate (LAS), which acts as a typical surfactant, the freshwater algae Scenedesmus obliquus was exposed to nZVI and LAS individually and in combination for 96 h. According to the inhibition rate of the algae, the toxic effects were investigated by dose-response analysis. Then the combined effect of nZVI and LAS was evaluated using three evaluation models including toxicity unit (TU), additional index (AI), and mixture toxicity index (MTI). The results showed that the 96 h IC50 of nZVI and LAS to Scenedesmus obliquus was 2.464 mmol L-1 and 0.332 mmol L-1, respectively. When nZVI coexisted with LAS at toxic ratio 1:1, the 96 h IC50 value was 1.658 mmol L-1 (shown with nZVI), and the partly additive effect of nZVI mixed with LAS was confirmed. However, when the toxic ratio of nZVI:LAS was 4:1, it showed synergistic effect. In addition, when nZVI mixed with LAS at toxic ratio 1:4, the joint effect is antagonistic effect. In addition, the content of chorophyll in Scenedesmus obliquus, especially the content of chlorophyll a, was decreased with the increase of mixture dose. However, the protein levels did not show significant changes at different mixture doses.

Superior trichloroethylene removal from water by sulfide-modified nanoscale zero-valent iron/graphene aerogel composite.

Sulfide-modified nanoscale zero-valent iron (S-nZVI) is a promising material for removal of organic pollutants from water, but S-nZVI nanoparticles (NPs) easily agglomerate and have poor contact with organic contaminants. Herein, we propose a new S-nZVI/graphene aerogel (S-nZVI/GA) composite which exhibits superior removal capability for trichloroethylene (TCE) from water. Three-dimensional porous graphene aerogel (GA) can improve the efficiency of electron transport, enhance the adsorption of organic pollutants and restrain the agglomeration of the core-shell S-nZVI NPs. The TCE removal rates of FeS, nZVI, GA and S-nZVI were 27.8%, 42%, 63% and 75% in 2 hr, respectively. Furthermore, TCE was completely removed within 50 min by S-nZVI/GA. The TCE removal rate increased with increasing pH and temperature, and TCE removal followed the pseudo-first-order kinetic model. The results demonstrate the great potential of S-nZVI/GA composite as a low-cost, easily separated and superior monolithic adsorbent for removal of organic pollutants.

Stabilization of nanoscale zero-valent iron in water with mesoporous carbon (nZVI@MC).

Two challenges persist in the applications of nanoscale zero-valent iron (nZVI) for environmental remediation and waste treatment: limited mobility due to rapid aggregation and short lifespan in water due to quick oxidation. Herein, we report the nZVI incorporated into mesoporous carbon (MC) to enhance stability in aqueous solution and mobility in porous media. Meanwhile, the reactivity of nZVI is preserved thanks to high temperature treatment and confinement of carbon framework. Small-sized (~16 nm) nZVI nanoparticles are uniformly dispersed in the whole carbon frameworks. Importantly, the nanoparticles are partially trapped across the carbon walls with a portion exposed to the mesopore channels. This unique structure not only is conductive to hold the nZVI tightly to avoid aggregation during mobility but also provides accessible active sites for reactivity. This new type of nanomaterial contains ~10 wt% of iron. The nZVI@MC possesses a high surface area (~500 m2/g) and uniform mesopores (~4.2 nm) for efficient pollutant diffusion and reactions. Also, high porosity of nZVI@MC contributes to the stability and mobility of nZVI. Laboratory column experiments further demonstrate that nZVI@MC suspension (~4 g Fe/L) can pass through sand columns much more efficiently than bare nZVI while the high reactivity of nZVI@MC is confirmed from reactions with Ni(II). It exhibits remarkably better performance in nickel (20 mg/L) extraction than mesoporous carbon, with 88.0% and 33.0% uptake in 5 min, respectively.

Preparation of porous semi-IPN temperature-sensitive hydrogel-supported nZVI and its application in the reduction of nitrophenol.

Nanoscale zero-valent iron (nZVI) particles supported on a porous, semi-interpenetrating (semi-IPN), temperature-sensitive composite hydrogel (PNIPAm-PHEMA). nZVI@PNIPAm-PHEMA, was successfully synthesized and characterized by FT-IR, SEM, EDS, XRD and the weighing method. The loading of nZVI was 0.1548 ±â€¯0.0015 g/g and the particle size was 30-100 nm. NZVI was uniformly dispersed on the pore walls inside the PNIPAm-PHEMA. Because of the well-dispersed nZVI, the highly porous structure, and the synergistic effect of PNIPAm-PHEMA, nZVI@PNIPAm-PHEMA showed excellent reductive activity and wide pH applicability. 95% of 4-NP in 100 mL of 400 mg/L 4-NP solution with initial pH 3.0-9.0 could be completely reduced into 4-AP by about 0.0548 g of fresh supported nZVI at 18-25 °C under stirring (110 r/min) within 45 min reaction time. A greater than 99% 4-NP degradation ratio was obtained when the initial pH was 5.0-9.0. The reduction of 4-NP by nZVI@PNIPAm-PHEMA was in agreement with the pseudo-first-order kinetics model with Kobs values of 0.0885-0.101 min-1. NZVI@PNIPAm-PHEMA was able to be recycled, and about 85% degradation ratio of 4-NP was obtained after its sixth reuse cycle. According to the temperature sensitivity of PNIPAm-PHEMA, nZVI@PNIPAm-PHEMA exhibited very good storage stability, and about 88.9% degradation ratio of 4-NP was obtained after its storage for 30 days. The hybrid reducer was highly efficient for the reduction of 2-NP, 3-NP, 2-chloro-4-nitrophenol and 2-chloro-4-nitrophenol. Our results suggest that PNIPAm-PHEMA could be a good potential carrier, with nZVI@PNIPAm-PHEMA having potential value in the application of reductive degradation of nitrophenol pollutants.

Feasibility of nanoscale zero-valent iron to enhance the removal efficiencies of heavy metals from polluted soils by organic acids.

Soil washing with natural chelators to remediate metal-contaminated soils has been gained attention by researchers. However, the abilities of the chelators to remediate the multiple metal polluted soils are less effective. This study employed zero-valent iron nanoparticle (nZVI) to enhance the removal efficiencies of citric (CA), tartaric (TA) and oxalic acids (OA), and evaluate their feasibility. Results showed that metal removal efficiencies increased with the increasing concentration of nZVI and soil-liquid ratio, decreased with the increasing solution pH. The kinetic simulation indicated that pseudo-first-order and pseudo-second-order models could be used for describing the washing processes. Additionally, metal removals were significantly improved by addition of nZVI (p < 0.05). The highest enhancements of soil Cd, Pb and Zn removals under solution pH of 4.0, soil-liquid ratio of 1:20 and washing time of 120 min reached 12.83% (OA- nZVI), 24.92% (CA-nZVI) and 11.64% (OA- nZVI) for mine soil, and 19.24% (TA- nZVI), 18.16% (CA-nZVI) and 8.93% (OA- nZVI) for farmland soil, respectively. After soil washing, the exchangeable forms and the environmental risks of residual metals were markedly diminished in soils. Therefore, the combinations of the organic acids and nZVI are the feasible practices to repair the soils contaminated by heavy metals.