Nanoscale Zero-Valent Iron(nZVI)for Heavy Metal Wastewater Treatment:A Perspective

Industries such as non-ferrous metal smelting discharge billions of gallons of highly toxic heavy metal wastewater(HMW)worldwide annually,posing a severe challenge to conventional wastewater treatment plants and harming the environment.HMW is traditionally treated via chemical precipitation using lime,caustic,or sulfide,but the effluents do not meet the increasingly stringent discharge standards.This issue has spurred an increase in research and the development of innovative treatment technologies,among which those using nanoparticles receive particular interest.Among such initiatives,treatment using nanoscale zero-valent iron(nZVI)is one of the best developed.While nZVI is already well known for its site-remediation use,this perspective highlights its application in HMW treatment with metal recovery.We demonstrate several advantages of nZVI in this wastewater application,including its multifunctionality in sequestrating a wide array of metal(loid)s(>30 species);its capability to capture and enrich metal(loid)s at low concentrations(with a removal capacity reaching 500 mg·g^(-1)nZVI);and its operational convenience due to its unique hydrodynamics.All these advantages are attributable to nZVI’s diminutive nanoparticle size and/or its unique iron chemistry.We also present the first engineering practice of this application,which has treated millions of cubic meters of HMW and recovered tons of valuable metals(e.g.,Cu and Au).It is concluded that nZVI is a potent reagent for treating HMW and that nZVI technology provides an eco-solution to this toxic waste.

Assessing the effectiveness of nanoscale zero-valent iron particles produced by green tea for Cr(VI)-contaminated groundwater remediation

Nanoscale zero-valent iron particles(NZVI) produced by using green tea(GT) extract as a reductant can remove Cr(Ⅵ) from water effectively,which can be utilized in groundwater remediation.In order to define the reaction mechanism and removal effect in the aquifer,in this study,GT-NZVI particles were prepared and measured by some characterization methods to define their surface performance,and then batch and one-dimensional experiments were carried out to reveal the reaction properties of GT-NZVI and Cr(Ⅵ) in groundwater.The results showed that the prepared GT-NZVI particles were regular spherical with a diameter of 10-20 nm,which could disperse in water stably.The main component of GT-NZVI wasα-Fe with superficial polyphenols as a stabilizer.GT-NZVI suspension had good ability to reduce the Cr(Ⅵ) to Cr(Ⅲ) in water.When the concentration of GT-NZVI was 1 g/L,the removal efficiency of Cr(Ⅵ)with an initial concentration of 100 mg/L reached 92.8% in 1 h reaction.In column tests,GT-NZVI passed through the natural sand column successfully with an average outflow percentage of 71.2%.The simulated in-situ reaction zone(IRZ) with GT-NZVI was used to remediate Cr(Ⅵ) contaminated groundwater.The oufflow concentration of Cr(Ⅵ) kept in 0.14-0.32 mg/L corresponding to the outflow rate below 0.32%within 15 days,and the removal efficiency of Cr(Ⅵ) by IRZ with GT-NZVI decreased with the increase of aquifer medium particle size,groundwater flow rate and ionic strength.Most of Cr(Ⅲ) as reduzate was adsorbed or immobilized on the surface or in the lattice of GT-NZVI,which indicated effective immobilization for chromium.

Biochar Supported Nanoscale Zero-valent Iron Composites for the Removal of Petroleum from Wastewater

Considering the need for efficiently and rapidly treating oily wastewater while preventing secondary pollution,the nanoscale zero-valent iron(nZVI)was supported on biochar prepared by using a spent mushroom substrate(SMS),to produce an iron-carbon composite(SMS-nZVI).The ability of the SMS-nZVI to treat wastewater containing high concentration of oil was then comprehensively evaluated.The morphology,structure,and other properties of the composite were characterized by using scanning electron microscopy,transmission electron microscopy,the Brunauer-Emmett-Teller nitrogen sorption analysis,and the Fourier transform infrared spectroscopy.The results show that the biochar prepared by using the SMS can effectively prevent the agglomeration of nZVI and increase the overall specific surface area,thereby enhancing the absorption of petroleum by the composite.Experiments reveal that compared with the SMS and nZVI,the SMS-nZVI composite removes petroleum faster and more efficiently from wastewater.Under optimized conditions involving an nZVI to biochar mass ratio of 1:5 and a pH value of 4,the efficiency for removal of petroleum from wastewater with an initial petroleum concentration of 1000 mg/L could reach 95%within 5 h.Based on a natural aging treatment involving exposure to air for 30 d,the SMS-nZVI composite retained an oil removal rate of higher than 62%,and this result could highlight its stability for practical applications.

Synthesis of clay-supported nanoscale zero-valent iron using green tea extract for the removal of phosphorus from aqueous solutions

This study addresses the synthesis of nanoscale zero-valent iron(n ZVI) in the presence of natural bentonite(B-n ZVI) using green tea extract. The natural bentonite and B-n ZVI were then applied for the removal of phosphorus from aqueous solutions at various concentrations, p H levels and contact time. The desorption of phosphorus(P) from adsorbents was done immediately after sorption at the maximum initial concentration using the successive dilution method. The characterization of FTIR, SEM, and XRD indicated that n ZVI was successfully loaded to the surface of natural bentonite. The sorption of phosphorus on B-n ZVI was observed to be p H-dependent, with maximum phosphorus removal occurring at the p H range of 2 to 5. The results demonstrate that the maximum sorption capacities of natural bentonite and B-n ZVI were 4.61 and 27.63 mg·g^(-1), respectively.Langmuir, Freundlich, and Redlich–Peterson models properly described the sorption isotherm data. For either adsorbent, desorption isotherms did not coincide with their corresponding sorption isotherms, suggesting the occurrence of irreversibility and hysteresis. The average percentages of retained phosphorus released from natural bentonite and B-n ZVI were 80% and 9%, respectively. The results indicated that sorption kinetics was best described by the pseudo-second-order model. The present study suggests that B-n ZVI could be used as a suitable adsorbent for the removal of phosphorus from aqueous solutions.

Corrosion behaviors and kinetics of nanoscale zero-valent iron in water:A review

Knowledge on corrosion behaviors and kinetics of nanoscale zero-valent iron(nZVI)in aquatic environment is particularly significant for understanding the reactivity,longevity and stability of nZVI,as well as providing theoretical guidance for developing a cost-effective nZVI-based technology and designing large-scale applications.Herein,this review gives a holistic overview on the corrosion behaviors and kinetics of nZVI in water.Firstly,Eh-pH diagram is introduced to predict the thermodynamics trend of iron corrosion.The morphological,structural,and compositional evolution of(modified-)nZVI under different environmental conditions,assisted with microscopic and spectroscopic evidence,is then summarized.Afterwards,common analytical methods and characterization technologies are categorized to establish time-resolved corrosion kinetics of nZVI in water.Specifically,stable models for calculating the corrosion rate constant of nZVI as well as electrochemical methods for monitoring the redox reaction are discussed,emphasizing their capabilities in studying the dynamic iron corrosion processes.Finally,in the future,more efforts are encouraged to study the corrosion behaviors of nZVI in long-term practical application and further build nanoparticles with precisely tailored properties.We expect that our work can deepen the understanding of the nZVI chemistry in aquatic environment.

Amino acids modified nanoscale zero-valent iron:Density functional theory calculations,experimental synthesis and application in the Fenton-like degradation of organic solvents

To improve the adsorption and catalytic performance of heterogeneous Fenton-like catalysts for oil wastes,amino acids were used to modify nanoscale zero-valent iron(AA@Fe^(0)),which were applied in the Fenton-like degradation of organic solvents(tributyl phosphate and n-dodecane,named TBP and DD).Twelve amino acids,i.e.,glycine(Gly),alanine(Ala),leucine(Leu),proline(Pro),phenylalanine(Phe),methionine(Met),cysteine(Cys),asparagine(Asn),serine(Ser),glutamic acid(Glu),lysine(Lys)and arginine(Arg),were selected and calculated by density functional theory(DFT).The optimized structure,charge distribution,the highest occupied molecular orbital(HOMO),the lowest unoccupied molecular orbital(LUMO),interaction region indicator(IRI)isosurface map and adsorption energy of AA@Fe^(0),AA@Fe^(0)-TBP and AA@Fe^(0)-DD were studied,which indicated that Fe is more likely to approach and charge transfer with-COO and-NH_(3) on theα-carbon of amino acids.There is strong attraction between Fe and–COO,and Van der Waals force between Fe and-NH_(3),respectively.In the interaction of AA@Fe^(0)with TBP and DD,Van der Waal force plays an important role.AA@Fe^(0)was synthesized in laboratory and characterized to investigate physicochemical properties.In Fenton-like degradation of organic solvents,the change of COD in water phase during the degradation process as well as the volume of the organic phase after the reaction were investigated.The results of calculations combined with experiments showed that Ser-modified Fe^(0)performed the best in these amino acids,with 98%removal of organic solvents.A possible catalytic mechanism was proposed in which amino acids acted a linking role between Fe and organic solvents,activating H_(2)O_(2)to generate hydroxyl radicals for the degradation of organic solvents.

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 involvedπ-πinteraction,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 Fe^(3+)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.

Unraveling biochar surface area on structure and heavy metal removal performances of carbothermal reduced nanoscale zero-valent iron

Carbothermal reduction using biochar(BC)is a green and effective method of synthesizing BCsupported nanoscale zero-valent iron(nanoFe^(0))composites.However,the effect of BC surface area on the structure,distribution,and performance such as the heavy metal uptake capacity of nanoFe^(0)particles remains unclear.Soybean stover-based BCs with different surface areas(1.7−1472 m^(2)/g)were prepared in this study.They have been used for in-situ synthesis BCs-supported nanoFe^(0)particlesthrough carbothermal reduction of ferrous chloride.The BCs-supported nanoFe^(0)particles were found to be covered with graphene shells and dispersed onto BC surfaces,forming the BC-supported graphene-encapsulated nanoFe^(0)(BC-G@Fe^(0))composite.These graphene shells covering the nanoFe^(0)particles were formed because of gaseous carbon evolved from biomass carbonization reacting with iron oxides/iron salts.Increasing BC surface area decreased the average diameters of nanoFe^(0)particles,indicating a higher BC surface area alleviated the aggregation of nanoFe^(0)particles,which resulted in higher heavy metal uptake capacity.At the optimized condition,BC-G@Fe^(0)composite exhibited uptake capacities of 124.4,121.8,254.5,and 48.0 mg/g for Cu^(2+),Pb^(2+),Ag^(+),and As^(3+),respectively(pH 5,25℃).Moreover,the BC-G@Fe^(0)composite also demonstrated high stability for Cu^(2+)removal from the fixed-bed continuous flow,in which 1 g of BC-G@Fe^(0)can work for 120 h in a 4 mg/L Cu^(2+)flow continually and clean 28.6 L Cu^(2+)contaminated water.Furthermore,the BC-G@Fe^(0)composite can effectively immobilize the bioavailable As^(3+)from the contaminated soil,i.e.,5%(w)of BC-G@Fe^(0)composite addition can immobilize up to 92.2%bioavailable As^(3+)from the contaminated soil.

Decolorization of Methyl Orange by a new clay-supported nanoscale zero-valent iron:Synergetic effect,efficiency optimization and mechanism

In this study, a novel nanoscale zero-valent iron（n ZVI） composite material was successfully synthesized using a low-cost natural clay, ＂Hangjin 2~#clay＂（HJ clay） as the support and tested for the decolorization of the azo dye Methyl Orange（MO） in aqueous solution by n ZVI particles. According to the characterization and MO decolorization experiments, the sample with 5：1 HJ clay-supported n ZVI（HJ/n ZVI） mass ratio（HJ-n ZVI5） showed the best dispersion and reactivity and the highest MO decolorization efficiency. With the same equivalent Fe0 dosage, the HJ-n ZVI1 and HJ-n ZVI5 samples demonstrated a synergetic effect for the decolorization of MO： their decolorization efficiencies were much higher than that achieved by physical mixing of HJ clay and n ZVIs, or the sum of HJ clay and n ZVIs alone. The synergetic effect was primarily due to the improved dispersion and more effective utilization of the n ZVI particles on/in the composite materials. Higher decolorization efficiency of MO was obtained at larger HJ-n ZVI dosage, higher temperature and under N2 atmosphere, while the MO initial concentration and p H were negatively correlated to the efficiency. HJ clay not only works as a carrier for n ZVI nanoparticles, but also contributes to the decolorization through an ＂adsorption-enhanced reduction＂ mechanism. The high efficiency of HJ-n ZVI for decontamination gives it great potential for use in a variety of remediation applications.

Humic acid and metal ions accelerating the dechlorination of 4-chlorobiphenyl by nanoscale zero-valent iron

Transformation of polychlorinated biphenyls （PCBs） by zero-valent iron represents one of the latest innovative technologies for environmental remediation. The dechlorination of 4-chlorobiphenyl （4-C1BP） by nanoscale zero-valent iron （NZVI） in the presence of humic acid or metal ions was investigated. The results showed that the dechlorination of 4-C1BP by NZVI increased with decreased solution pH. When the initial pH value was 4.0, 5.5, 6.8, and 9.0, the de.chlorination efficiencies of 4-CIBP after 48 hr were 53.8%, 47.8%, 35.7%, and 35.6%, respectively. The presence of humic acid inhibited the reduction of 4-CIBP in the first 4 hi＇, and then significantly accelerated the dechlorination by reaching 86.3% in 48 hr. Divalent metal ions, Co2＋, Cu2＋, and Ni2＋, were reduced and formed bimetals with NZVI, thereby enhanced the dechlorination of 4-CIBP. The dechlorination percentages of 4-CIBP in the presence of 0.1 mmol/L Co2~, Cuz~ and Niz~ were 66.1%, 66.0% and 64.6% in 48 hr, and then increased to 67.9%, 71.3% and 73.5%, after 96 hr respectively. The dechlorination kinetics of 4-C1BP by the NZVI in all cases followed pseudo-first order model. The results provide a basis for better understanding of the dechlorination mechanisms of PCBs in real environment.

Nanoencapsulation of hexavalent chromium with nanoscale zero-valent iron:High resolution chemical mapping of the passivation layer

Solid phase reactions of Cr（Ⅵ） with Fe（0） were investigated with spherical-aberration-corrected scanning transmission electron microscopy（Cs-STEM） integrated with X-ray energy-dispersive spectroscopy（XEDS）. Near-atomic resolution elemental mappings of Cr（Ⅵ）–Fe（0） reactions were acquired. Experimental results show that rate and extent of Cr（Ⅵ） encapsulation are strongly dependent on the initial concentration of Cr（Ⅵ） in solution. Low Cr loading in nZⅥ（〈1.0 wt%） promotes the electrochemical oxidation and continuous corrosion of n ZⅥ while high Cr loading（〉1.0 wt%） can quickly shut down the Cr uptake. With the progress of iron oxidation and dissolution, elements of Cr and O counter-diffuse into the nanoparticles and accumulate in the core region at low levels of Cr（Ⅵ）（e.g., 〈 10 mg/L）. Whereas the reacted n ZⅥ is quickly coated with a newly-formed layer of 2–4 nm in the presence of concentrated Cr（Ⅵ）（e.g., 〉 100 mg/L）. The passivation structure is stable over a wide range of pH unless pH is low enough to dissolve the passivation layer. X-ray photoelectron spectroscopy（XPS） depth profiling reconfirms that the composition of the newly-formed surface layer consists of Fe（Ⅲ）–Cr（Ⅲ）（oxy）hydroxides with Cr（Ⅵ） adsorbed on the outside surface. The insoluble and insulating Fe（Ⅲ）–Cr（Ⅲ）（oxy）hydroxide layer can completely cover the n ZⅥ surface above the critical Cr loading and shield the electron transfer. Thus, the fast passivation of nZⅥ in high Cr（Ⅵ） solution is detrimental to the performance of nZⅥ for Cr（Ⅵ） treatment and remediation.

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 biotechnologies. 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.

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

Sodium citrate(SC)is a widely-used food and industrial additive with the properties of com-plexation 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 solu-tions.The nZVI,SC-nZVI and SC-nZVI@BC were characterized and compared using X-ray diffraction(XRD),Fourier transform infrared spectroscopy(FTIR),thermogravimetric analy-ses(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 pas-sivation 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℃,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 demon-strated that the SC-nZVI@BC exhibited excellent removal efficiency toward Cr(Ⅵ)with an improved synergistic characteristic by SC and BC.

Debromination of decabromodiphenyl ether by organo-montmorillonitesupported nanoscale zero-valent iron: Preparation, characterization and influence factors

An organo-montmorillonite-supported nanoscale zero-valent iron material （M-NZVI） was synthesized to degrade decabromodiphenyl ether （BDE-209）. The results showed that nanoscale zero-valent iron had good dispersion on organo-montmoriUonite and was present as a core-shell structure with a particle size range of nanoscale iron between 30-90 nm, characterized by XRD, SEM, TEM, XRF, ICP-AES, and XPS. The results of the degradation of BDE-209 by M-NZVI showed that the efficiency of M-NZVI in removing BDE-209 was much higher than that of NZVI. The efficiency of M-NZVI in removing BDE-209 decreased as the pH and the initial dissolved oxygen content of the reaction solution increased, but increased as the proportion of water in the reaction solution increased.

Cation exchange resin supported nanoscale zero-valent iron for removal of phosphorus in rainwater runoff

Self-made cation exchange resin supported nanoscale zero-valent iron （R-nZVI） was used to remove phosphorus in rainwater runoff. 80% of phosphorus in rainwater runoff from grassland was removed with an initial concentration of 0.72 mg. L-1 phosphorus when the dosage of R-nZVl is 8 g per liter rainwater, while only 26% of phosphorus was removed when using cation exchange resin without supported nanoscale zero-valent iron under the same condition. The adsorption capacity of R-nZVI increased up to 185 times of that of the cation exchange resin at a saturated equilibrium phosphorous concentration of 0.42 mg. L-1. Various techniques were implemented to characterize the R-nZVI and explore the mechanism of its removal of phosphate. Scanning electron microscopy （SEM） indicated that new crystal had been formed on the surface of R-nZVI. The result from inductive coupled plasma （ICP） indicated that 2.1% of nZVI was loaded on the support material. The specific surface area was increased after the load of nanoscale zero-valent iron （nZVI）, according to the measurement of BET-N2 method. The result of specific surface area analysis also proved that phosphorus was removed mainly through chemical adsorption process. X-ray photoelectron spectroscopy （XPS） analysis showed that the new product obtained from chemical reaction between phosphate and iron was ferrous phosphate.

The colorful chemistry of nanoscale zero-valent iron(nZVI)

Nanoscale zero-valent iron （nZVI） possesses unique chemistry and capability for the separation and transformation of a growing number of environmental contaminants. A nZVI particle consists of two nanoscale components, an iron （oxyhydr）oxides shell and a metallic iron core. This classical ＂core-shell＂ structure offers nZVI with unique and multifaceted reactivity of sorption, complexation, reduction and precipita- tion due to its strong small particle size for engineering deployment, large surface area, abundant reactive sites and electron-donating capacity for enhanced chemical activity. For over two decades, research has been steadily expanding our understanding on the reaction mechanisms and engineering performance of nZVI for soil and groundwater remediation, and more recently for wastewater treatment.

Degradation of chlorinated phenols by nanoscale zero-valent iron

Chlorophenols(CPs),as important contami-nants in groundwater,are toxic and difficult to biode-grade.Recentlynanoscalezero-valentironreceivedagreat deal of attention because of its excellent performance in treating recalcitrant compounds.In this study,nanoscale zero-valent iron particles were prepared using chemical reduction,and the reductive transformations of three kinds of chlorinated phenols(2-CP,3-CP,and 4-CP)by nanoscale zero-valent iron under different conditions were investigated.The transformation process of the CPs was shown to be dechlorination first,then cleavage of the benzene ring.The removal efficiency of the CPs varied as follows:2-CP.3-CP.4-CP.The reactivity of CPs was associated with their energy of lowest unoccupied molecular orbit(E LUMO).With the increase in initial concentrations of CPs,removal efficiency decreased a little.But the quantities of CPs reduced increased evidently.Temperature had influence on not only the removal efficiency,but also the transformation pathway.At higher temperatures,dechlorination occurred prior to benzene ring cleavage.At lower temperatures,however,the oxidation product was formed more easily.

The inactivation of bacteriophages MS2 and PhiX174 by nanoscale zero-valent iron:Resistance difference and mechanisms

Pathogenic enteric viruses pose a significant risk to human health.Nanoscale zero-valent iron(nZVI),a novel material for environmental remediation,has been shown to be a promising tool for disinfection.However,the existing research has typically utilized MS2 or f2 bacteriophages to investigate the antimicrobial properties of nZVI,and the resistance difference between bacteriophages,which is important for the application of disinfection technologies,is not yet understood.Here,MS2 and PhiX174 containing RNA and DNA,respectively,were used as model viruses to investigate the resistances to nZVI.The bacteriophage inactivation mechanisms were also discussed using TEM images,protein,and nucleic acid analysis.The results showed that an initial concentration of 10^(6)PFU/mL of MS2 could be completely inactivated within 240 min by 40 mg/L nZVI at pH 7,whereas the complete inactivation of PhiX174 could not be achieved by extending the reaction time,increasing the nZVI dosage,or changing the dosing means.This indicates that the resistance of phage PhiX174 to nZVI was much stronger than that of MS2.TEM images indicated that the viral particle shape was distorted,and the capsid shell was ruptured by nZVI.The damage to viral surface proteins in both phages was examined by three-dimensional fluorescence spectrum and sodium dodecyl sulfate polyacrylamide gel electrophoresis(SDS-PAGE).However,the nucleic acid analysis demonstrated that the nucleic acid of MS2,but not PhiX174,was destroyed.It indicated that bacteriophage inactivation was mainly attributed to the damage of nucleic acids.

Performance of bimetallic nanoscale zero-valent iron particles for removal of oxytetracycline

In this study, bimetallic nanoscale zero-valent iron particles（nZVI）, including copper/nanoscale zero-valent iron particles（Cu/nZVI） and nickel/nanoscale zero-valent iron particles（Ni/nZVI）, were synthesized by one-step liquid-phase reduction and applied for oxytetracycline（OTC） removal. The effects of contact time and initial p H on the removal efficiency were studied. The as-prepared nanoscale particles were characterized by scanning electron microscopy（SEM）, energy dispersive spectroscopy（EDS） and X-ray diffraction（XRD）. Finally, the degradation mechanisms of OTC utilizing the as-prepared nanoparticles were investigated by using X-ray photoelectron spectroscopy（XPS） and mass spectrometry（MS）. Cu/n ZVI presented remarkable ability for OTC degradation and removed71.44% of OTC（100 mg/L） in 4 hr, while only 62.34% and 31.05% of OTC was degraded by Ni/nZVI and nZVI respectively. XPS and MS analysis suggested that OTC was broken down to form small molecules by ·OH radicals generated from the corrosion of Fe0. Cu/nZVI and Ni/n ZVI have been proved to have potential as materials for application in OTC removal because of their significant degradation ability toward OTC.

Nanoencapsulation of arsenate with nanoscale zero-valent iron(nZVI):A 3D perspective

The principal forces driving the efficient enrichment and encapsulation of arsenic(As) into nanoscale zero-valent iron(nZVI) are the disordered arrangement of the atoms and the gradient chemical potentials within the core-shell interface. The chemical compositions and the fine structure of nZVI are characterized with a combination of spherical aberration corrected scanning transmission electron microscopy(Cs-STEM), X-ray energy-dispersive spectroscopy(XEDS), electron energy loss spectroscopy(EELS), and high-resolution X-ray photoelectron spectroscopy(HR-XPS). Atomically resolved EELS at the oxygen K-edge unfolds that the Fe species in nZVI are well stratified from Fe(Ⅲ) oxides in the outermost periphery to a mixed Fe(Ⅲ)/Fe(Ⅱ) interlayer, then Fe(Ⅱ) oxide and the pure Fe(0) phase. Reactions between As(Ⅴ)and nZVI suggest that a well-structured local redox gradient exists within the shell layer, which serves as a thermodynamically favorable conduit for electron transfer from the iron core to the surface-bound As(Ⅴ). HR-XPS with ion sputtering shows that arsenic species shift from As(Ⅴ), As(Ⅲ)/As(Ⅴ) to As(Ⅴ)/As(Ⅲ)/As(0) from the iron oxide shell–water interface to the Fe(0) core. Results reinforce previous work on the efficacy of nZVI for removing and remediating arsenic while the analytical TEM methods are also applicable to the study of environmental interfaces and surface chemistry.