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.

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.

Treatment of simulated wastewater containing Reactive Red 195 by zero-valent iron/activated carbon combined with microwave discharge electrodeless lamp/sodium hypochlorite

A comparative study of treatment of simulated wastewater containing Reactive Red 195 using zero-valent iron/activated carbon （ZVI/AC）, microwave discharge electrodeless lamp/sodium hypochlorite （MDEL/NaCIO） and the combination of ZVI/AC- MDEL/NaCIO was conducted. The preliminary results showed the two steps method of ZVI/AC-MDEL/NaCIO had much higher degradation efficiency than both single steps. The final color removal percentage was nearly up to 100% and the chemical oxygen demand reduction percentage was up to approximately 82%. The effects of operational parameters, including initial pH value of simulated wastewater, ZVI/AC ratio and particle size of ZVI were also investigated. In addition, from the discussion of synergistic effect between ZVI/AC and MEDL/NaCIO, we found that in the ZVI/AC-MEDL/NaCIO process, ZVI/AC could break the azo bond firstly and then MEDLfNaCIO degraded the aromatic amine products effectively. Reversing the order would reduce the degradation efficiency.

Enhanced recovery of high-purity Fe powder from iron-rich electrolytic manganese residue by slurry electrolysis

Iron-rich electrolytic manganese residue(IREMR)is an industrial waste produced during the processing of electrolytic metal manganese,and it contains certain amounts of Fe and Mn resources and other heavy metals.In this study,the slurry electrolysis technique was used to recover high-purity Fe powder from IREMR.The effects of IREMR and H2SO4 mass ratio,current density,reaction temper-ature,and electrolytic time on the leaching and current efficiencies of Fe were studied.According to the results,high-purity Fe powder can be recovered from the cathode plate,and the slurry electrolyte can be recycled.The leaching efficiency,current efficiency,and purity of Fe reached 92.58%,80.65%,and 98.72wt%,respectively,at a 1:2.5 mass ratio of H2SO4 and IREMR,reaction temperature of 60℃,electric current density of 30 mA/cm^(2),and reaction time of 8 h.In addition,vibrating sample magnetometer(VSM)analysis showed that the coercivity of electrolytic iron powder was 54.5 A/m,which reached the advanced magnetic grade of electrical pure-iron powder(DT4A coercivity standard).The slurry electrolytic method provides fundamental support for the industrial application of Fe resource recovery in IRMER.

Eco friendly adsorbents for removal of phenol from aqueous solution employing nanoparticle zero-valent iron synthesized from modified green tea bio-waste and supported on silty clay

The present research investigated a novel route for the synthesis of nanoparticle zero-valent iron(NZVI)utilizing an aqueous extract of green tea waste as a reductant with ferric chloride.Also,the supported nanoparticle zerovalent iron was synthesized using natural silty clay as a support material(SC-NZVI).The NZVI and SC-NZVI were characterized by infrared spectroscopy(FTIR),scanning electron microscope(SEM),X-ray diffraction(XRD),Brunauer–Emmett–Teller(BET),and zeta potential(ζ).The interpretation of the results demonstrated that the polyphenol and other antioxidants in green tea waste can be used as reduction and capping agents in NZVI synthesis,with silty clay an adequate support.Additionally,the experiments were carried out to explore phenol adsorption by NZVI and SC-NZVI.To determine the optimum conditions,the impact of diverse experimental factors(i.e.,initial pH,adsorbent dose,temperature,and concentration of phenol)was studied.Langmuir,Freundlich,and Tempkin isotherms were used as representatives of adsorption equilibrium.The obtained results indicated that the adsorption processes for both NZVI and SC-NZVI well fitted by the Freundlich isotherm model.The appropriateness of pseudofirstorder and pseudosecondorder kinetics was investigated.The experimental kinetics data were good explained by the second-order model.The thermodynamic parameters(ΔH0,ΔS0,andΔG0)for NZVI and SC-NZVI were determined.The maximum removal rates of phenol at optimum conditions,when adsorbed onto NZVI and SC-NZVI,were found to be 94.8%and 90.1%,respectively.

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.

Study of diclofenac removal by the application of combined zero-valent iron and calcium peroxide nanoparticles in groundwater

Diclofenac(DCF)is one of the most frequently detected pharmaceuticals in groundwater,posing a great threat to the environment and human health due to its toxicity.To mitigate the DCF contamination,experiments on DCF degradation by the combined process of zero-valent iron nanoparticles(nZVI)and nano calcium peroxide(nCaO_(2))were performed.A batch experiment was conducted to examine the influence of the adding dosages of both nZVI and nCaO_(2)nanoparticles and pH value on the DCF removal.In the meantime,the continuous-flow experiment was done to explore the sustainability of the DCF degradation by jointly adding nZVI/nCaO_(2)nanoparticles in the reaction system.The results show that the nZVI/nCaO_(2)can effectively remove the DCF in the batch test with only 0.05 g/L nZVI and 0.2 g/L nCaO_(2)added,resulting in a removal rate of greater than 90%in a 2-hour reaction with an initial pH of 5.The degradation rate of DCF was positively correlated with the dosage of nCaO_(2),and negatively correlated with both nZVI dosage and the initial pH value.The order of significance of the three factors is identified as pH value>nZVI dosage>nCaO_(2)dosage.In the continuous-flow reaction system,the DCF removal rates remained above 75%within 150 minutes at the pH of 5,with the applied dosages of 0.5 g/L for nZVI and 1.0 g/L for nCaO_(2).These results provide a theoretical basis for the nZVI/nCaO_(2)application to remove DCF in groundwater.

Enhanced degradation of carbon tetrachloride by surfactant-modified zero-valent iron

Sorption of carbon tetrachloride （CT） by zero-valent iron （ZVI） is the rate-limiting step in the degradation of CT, so the sorption capacity of ZVl is of great importance. This experiment was aimed at enhancing the sorption of CT by ZVI and the degradation rate of CT by modification of surfactants. This study showed that ZVI modified by cationic surfactants has favorable synergistic effect on the degradation of CT. The CT degradation rate of ZVI modified by cetyl pyridinium bromide （CPB） was higher than that of the unmodified ZVI by 130%, and the CT degradation rate of ZVI modified by cetyl trimethyl ammonium bromide （CTAB） was higher than that of the unmodified ZVI by 81%. This study also showed that the best degradation effect is obtained at the near critical micelle concentrations （CMC） and that high loaded cationic surfactant does not have good synergistic effect on the degradation due to its hydrophilicity and the block in surface reduction sites. Furthermore degradation of CT by ZVI modified by nonionic surfactant has not positive effect on the degradation as the ionic surfactant and the ZVI modified by anionic surfactant has hardly any obvious effects on the degradation.

H₂Gas Charging of Zero-Valent Iron and TCE Degradation

Granular zero-valent iron (ZVI) has been widely used to construct permeable reactive barriers (PRB) for the in situ remediation of groundwater contaminated with halogenated hydrocarbons. In the anaerobic condition of most groundwater flow systems, iron undergoes corrosion by water and results in hydrogen gas generation. Several studies have shown that some of the hydrogen gas generated at the iron/water interface can diffuse into the iron lattice. Hydrogen gas also can be an electron donor for dechlorination of chlorinated compounds. In this study, the possibility of hydrogen gas bound in the lattice of ZVI playing a role in dehalogenation and improving the degradation efficiency of ZVI was evaluated. Two different granular irons were tested: one obtained from Quebec Metal Powders Ltd (QMP) and the other from Connelly-GPM. Ltd. For each type of iron, two samples were mixed with water and sealed in testing cells. Since the rate of hydrogen entry varies directly with the square root of the hydrogen pressure, one sample was maintained for several weeks under near-vacuum conditions to minimize the amount of hydrogen entering the iron lattice. The other sample was maintained for the same period at a hydrogen pressure of over 400 kPa to maximize the amount of hydrogen entering the iron lattice. The degradation abilities of the reacted ironsand the original iron materials were tested by running several sets of batch tests. The results of this study show little to no improvement of inorganic TCE degradation reactions due to the presence of lattice-stored hydrogen in iron material. This is probably due to the high energiesrequired to release hydrogen trapped in the iron lattice. However, there are certain chemical compounds that can promote hydrogen release from the iron lattice, and there may be bacteria that can utilize lattice-bound hydrogen to carry out dechlorination reactions.

Remediation of Nitrate and ChromiumContaminated Groundwater by Zero-valent IronPRB

Through continuous flow experimentation, the reactivity characteristics of zero-valent iron （Fe0）-PRB with ground watercontaminated by nitrate, chromium and the combination of nitrate and chromium were investigated. The results showed thatnitrate could be effectively deoxidized by zero-valent iron. NO^2- -N was the transitional deoxidization product, while NH4＋-Nwas the main final product in the effluent. Chromium could be deoxidized by zero-valent iron more effectively for the chromiumcontaminated ground water which was treated by PRB. The redox products such as Fe3＋ and Cr（III） precipitated on the packingmedia during the process. For the treatment of ground water contaminated by both nitrate and chromium, the results showed thatthe Cr（VI） removal efficiency by the zero-valent iron was not affected by the co-existence of NO^3- -N, while the NO^3- -N removalefficiency decreased with the existence of Cr（VI）.

Kinetics and corrosion products of aqueous nitrate reduction by iron powder without reaction conditions control

Although considerable research has been conducted on nitrate reduction by zero-valent iron powder （Fe^0）, these studies were mostly operated under anaerobic conditions with invariable pH that was unsuitable for practical application. Without reaction conditions （dissolved oxygen or reaction pH） control, this work aimed at subjecting the kinetics of denitrification by microscale Fe^0 （160-200 mesh） to analysis the factors affecting the denitrification of nitrate and the composition of iron reductive products coating upon the iron surface. Results of the kinetics study have indicated that a higher initial concentration of nitrate would yield a greater reaction rate constant. The reduction rate of nitrate increased with increasing Fe^0 dosage. The reaction can be described as a pseudo-first order reaction with respect to nitrate concentration or Fe^0 dosage. Experimental results also suggested that nitrate reduction by microscale Fe^0 without reaction condition control primarily was an acid-driven surface-mediated process, and the reaction order was 0.65 with respect to hydrogen ion concentration. The analyses of X-ray diffractometry and X-ray photoelectron spectroscopy indicated that a black coating, consisted of Fe2O3, Fe3O4 and FeO（OH）, was formed on the surface of iron grains as an iron corrosion product when the system initial pH was lower than 5. The proportion of FeO（OH） increased as reaction time went on, whereas the proportion of Fe3O4 decreased.

Improved model and 3D simulation of densification process for iron powder

A new model for describing the compaction process of iron powder was proposed based on the continuum hypothesis and elliptical yield criterion.To simulate the densification behaviour,the constitutive model was implemented in Marc computer program.For the relationship between load and displacement,different models were compared and the influence of the parameters in the constitutive equations was determined by means of simulation and experiments.The density distribution of a balancer was measured and simulated.The results show that the parameterηadopted plays a modification role for the load-displacement curve,and compared with other models the present model fits better with the experimental data in the later stage of the compaction process mainly due to the different parameters A and B.The friction on the contact surface contributes to the inhomogeneous density distribution under large deformation of the workpiece.The comparison between the simulation and experimental data indicates that this model can be used to predict the powder compact process precisely and effectively.

Analysis of density and mechanical properties of high velocity compacted iron powder

A new method for producing higher density PM parts, high velocity compaction （HVC）, was presented in the paper. Using water atomized pure iron powder without lubricant admixed as the staring material, ring samples were compacted by the technique. Scanning electron microscopy （SEM） and a computer controlled universal testing machine were used to investigate the morphologies and the mechanical properties of samples, respectively. The relationships among the impact velocity, the green density, the sintered density, the bending strength and the tensile strength were discussed, The results show that with increasing impact velocity, the green density and the bending strength increase gradually, so the sintered density does. In addition, the tensile strength of sintered material is improved continuously with the sintered density enhancing. In the study, the sintered density of 7.545 g/cm^3 and the tensile strength of 190 MPa are achieved at the optimal impact velocity of 9.8 m/s.

Production of Reduced Iron Powder Using Ultra-Fine Iron Concentrate

The using of the iron to extract reduced iron with T Fe ≥ 69.5% Al 2O 3+SiO 2<0.3% was studied. Preparation of reduced iron powder in this experimental research can produce ultra pure magnetite concentrate. The quality of the final product reaches the product standard of SC 100.26 and NC 100.24.

Improving chill control in iron powder treated slightly hypereutectic grey cast irons

Recent studies revealed that in eutectic to slightly hypereutectic grey irons （CE = 4.3%-4.5%） the presence of austenite dendrites provides an opportunity to improve the cast iron properties, as a high number of eutectic cells are ＂reinforced＂ by austenite dendrites. An iron powder addition proved to be important by promoting dendritic austenite in hypereutectic irons, but was accompanied by adverse effect on the characteristics of potential nuclei for graphite. The purpose of the present paper is to investigate the solidification pattern of these irons. Chill wedges with different cooling moduli （CM = 0.11 - 0.43 cm） were poured in resin bonded sand and metal moulds. Relative clear / mottled / total chill measurement criteria were applied. Iron powder additions led to a higher chill tendency, while single inoculation showed the strongest graphiUzing effect. The various double treatments show an intermediate position, but the inoculant added after iron powder appears to be the most effective in reducing base iron chill tendency, for all cooling moduli and chill evaluation parameters. This performance reflects the improved properties of （Mn,X）S polygonal compounds as nucleation sites for graphite, especially in resin bonded sand mould castings. Both austenite and graphite nucleation benefit from a double addition of iron powder ＋ inoculant, with positive effect on the final structure and chill tendency.

Surfactant-assisted removal of 2,4-dichlorophenol from soil by zero-valent Fe/Cu activated persulfate

The organic compounds contaminated soil substantially threatens the growth of plants and food safety.In this study,we synthesis zero-valent bimetallic Fe/Cu catalysts for the degradation of 2,4-dichlorophenol(DCP)in soils with persulfate(PS)in combination of organic surfactants and exploring the main environmental impact factors.The kinetic experiments show that the 5%(mass)dosage of Fe/Cu exhibits a higher degradation efficiency(86%)of DCP in soils,and the degradation efficiency of DCP increases with the increase of the initial PS concentration.Acidic conditions are favorable for the DCP degradation in soils.More importantly,the addition of Tween-80,and Triton-100 can obviously desorb DCP from the soil surface,which enhances the degradation efficiency of DCP in soils by Fe/Cu and PS reaction system.Furthermore,the Quenching experiments demonstrate that SO_(4)^(-1)·and·OH are the predominant radicals for the degradation of DCP during the Fe/Cu and PS reaction system as well as non-radical also exist.The findings of this work provide an effective method for remediating DCP from soils.

Effect of Iron Powder (Fe₂O₃) on Strength, Workability, and Porosity of the Binary Blended Concrete

In this study, the effect of iron powder (Fe2O3) on the compressive strength, tensile strength, workability, and porosity of the binary blended concrete were experimentally investigated. For this purpose, Portland cement was partially replaced by 1.5%, 2.5%, 3.5%, and 5% by weighing of iron powder. The amount of water-binder-ratio was considered constant. The workability of the fresh composite concrete was determined using cone Abrams method;mechanical properties were determined included compressive and tensile strengths at 7, 14, and 28 days and durability evaluated by water absorption and permeable porosity. It was observed that the compressive and tensile strengths change with the replacement of iron powder by up to 5%. However, the maximum improvement was gained at 2.5 wt% for compressive strength and 1.5 wt% for tensile strength. The workability of the fresh mixtures decreased when iron powder amount increased. It was observed that the porosity decreased respectively by 21.88% and 26.77% at 1.5 wt% and 2.5 wt% replacement. Moreover, this present study shows the importance and benefits to improve concrete properties by using micro-particles materials.

Effect of Submicron SiO_(2) Powder Addition on Properties of Cement Free Iron Trough Castables

A new cement free iron trough castable was prepared with dense corundum and silicon carbide as the main raw materials and submicron SiO_(2) powder(d_(50)=0.242μm,SiO_(2)=99.9 mass%)as the binder.The effect of the submicron SiO_(2) powder addition(3%,4%,5%,6%,7%,8%,and 9%,by mass,respectively)on the properties of the prepared castables was studied.The working mechanism of submicron SiO_(2) powder was analyzed from the perspective of the particle size distribution and infrared absorption spectrum.The results show that:(1)cement free iron trough castables can be prepared using submicron SiO_(2) powder alone as the binder;(2)compared with traditional castables,the cement free castables have made a breakthrough in the water addition and hot modulus of rupture.The optimal submicron SiO_(2) powder addition is 4%-6%.

Die wall lubricated warm compaction of iron-based powder metallurgy material

Lubricant is harmful to the mechanical properties of the sintered materials. Die wall lubrication was applied on warm compaction powder metallurgy in the hope of reducing the concentration level of the admixed lubricant. Iron based samples were prepared by die wall lubricated warm compaction at 175 ℃, using a compacting pressure of 550 MPa. Emulsified polytetrafluoroethylene(PTFE) was used as die wall lubricant. Admixed lubricant concentration ranging from 0 to 0.5% was tested. Extremely low admixed lubricant contents were used. Results show that in addition to the decrease in ejection forces, the green density of the compacts increases with the decrease of admixed lubricant content until it reaches the maximum at 0.06% of lubricant content, then decreases with the decrease of admixed lubricant content. The mechanical properties of the sintered compacts that contain more than 0.06% admixed lubricant are better than those of the samples that contain lesser lubricant. No scoring was observed in all die wall lubricated experiments.

Remediation of Ni^(2+)-contaminated water using iron powder and steel manufacturing byproducts

Steel manufacturing byproducts and commercial iron powders were tested in the treatment of Ni^2＋-contaminated water. Ni^2＋ is a priority pollutant of some soils and groundwater. The use of zero-valent iron, which can reduce Ni^2＋ to its neural form appears to be an alternative approach for the remediation of Ni^2＋-contaminated sites. Our experimental data show that the removal efficiencies of Ni^2＋ were 95.15% and 94.68% at a metal to solution ratio of 20 g/L for commercial iron powders and the steel manufacturing byproducts in 60 min at room temperature, respectively. The removal efficiency reached 98.20% when the metal to solution ratio was 40 g/L for commercial iron powders. Furthermore, we found that the removal efficiency was also largely affected by other factors such as the pHs of the treated water, the length of time for the metal to be in contact with the Ni^2＋-contaminated water, initial concentrations of metal solutions, particle sizes and the amount of iron powders. Surprisingly, the reaction temperature appeared to have little effect on the removal efficiency. Our study opens the way to further optimize the reaction conditions of in situ remediation of Ni^2＋ or other heavy metals on contaminated sites.