The earthworm-based vermiremediation facilitated with benign chemicals such as nano zero-valent iron(nZVI)is a promising approach for the remediation of a variety of soil contaminants including cyanotoxins.As themost ...The earthworm-based vermiremediation facilitated with benign chemicals such as nano zero-valent iron(nZVI)is a promising approach for the remediation of a variety of soil contaminants including cyanotoxins.As themost toxic cyanotoxin,microcystin-LR(MC-LR)enter soil via runoff,irrigated surface water and sewage,and the application of cyanobacterial biofertilizers as part of the sustainable agricultural practice.Earthworms in such remediation systems must sustain the potential risk from both nZVI and MC-LR.In the present study,earthworms(Eisenia fetida)were exposed up to 14 days to MC-LR and nZVI(individually and inmixture),and the toxicity was investigated at both the organismal andmetabolic levels,including growth,tissue damage,oxidative stress,metabolic response and gut microbiota.Results showed that co-exposure of MC-LR and nZVI is less potent to earthworms than that of separate exposure.Histological observations in the co-exposure group revealed only minor epidermal brokenness,and KEGG enrichment analysis showed that co-exposure induced earthworms to regulate glutathione biosynthesis for detoxification and reduced adverse effects from MC-LR.The combined use of nZVI promoted the growth and reproduction of soil and earthworm gut bacteria(e.g.,Sphingobacterium and Acinetobacter)responsible for the degradation of MC-LR,whichmight explain the observed antagonism between nZVI and MC-LR in earthworm microcosm.Our study suggests the beneficial use of nZVI to detoxify pollutants in earthworm-based vermiremediation systems where freshwater containing cyanobacterial blooms is frequently used to irrigate soil and supply water for the growth and metabolism of earthworms.展开更多
Antimony(Sb)contamination in paddy fields can lead to its accumulation in rice grains,posing a threat to food safety.To address this issue,the combined use of zero-valent iron(ZVI)and biochar(BC)were applied to decrea...Antimony(Sb)contamination in paddy fields can lead to its accumulation in rice grains,posing a threat to food safety.To address this issue,the combined use of zero-valent iron(ZVI)and biochar(BC)were applied to decrease the uptake of Sb in Sb-polluted soils,and their effects on Sb uptake from soil to rice grains were investigated.Our results showed that the combination treatment of 0.05%ZVI and 0.095%BC resulted in a significant decrease(42.8%)in Sb accumulation in rice grains that was comparably more efficient than that by 0.05%ZVI(decrease of 15.8%Sb accumulation)or 0.095%BC(decrease of 12.7%Sb accumulation)alone,demonstrating the synergistic effect of ZVI and BC on mitigating Sb uptake by rice plants.ZVI presence resulted in the formation of iron oxides in the soil and on root surfaces,and the S^(2-)/S_(2)^(2-)ascent also increased by 58.7%on day 75 compared with that of the control,facilitating the reduction of Sb(Ⅴ)to less mobile Sb(Ⅲ),thereby decreasing Sb accumulation in rice plants.BC initially increased themobility of Sb owing to its alkaline nature,whereas the electron shuttle properties of BC contributed to a decrease in Sbmobility.The abundance of the arsenite-reducing gene arrA ultimately increased by 203.2% on day 120 compared with the initial phase on day 5,and BC caused a remarkable increase in arrA gene abundance.This study revealed the synergistic mechanisms by combining ZVI and BC to mitigate Sb uptake by rice,which may be useful for the sustainable remediation of contaminated rice paddies.展开更多
Clogging of zero-valent iron(ZVI)is among the most prominent technical bottlenecks limiting its application in long-term groundwater remediation.In this study,three ZVI species with different oxygenated anion modifica...Clogging of zero-valent iron(ZVI)is among the most prominent technical bottlenecks limiting its application in long-term groundwater remediation.In this study,three ZVI species with different oxygenated anion modifications on the surface—micron ZVI(mZVI),oxalated mZVI(OX-mZVI),and phosphorylated mZVI(P-mZVI)—were selected to conduct a comparative study on the clogging problem during remediation of nitrobenzene-contaminated groundwater.The clogging degree(ΦC)was innovatively employed to quantify ZVI clogging,and the clogging mechanisms of influencing factors were uncovered by analyzing changes inΦC,reactivity,volume expansion,iron valence state,and iron corrosion product(FeCP)species.Results revealed that the clogging resistance of ZVI decreased in the following order:P-mZVI>OX-mZVI>mZVI.The reduction process of nitrobenzene controlled the increase ofΦC,and the reduction of NO_(3)^(−)—a groundwater background ion—served as an indicator for clogging stage changes.Surface chemistry analysis revealed that the increase ofΦC originated from the volume expansion effect of FeCPs.Iron corrosion increased the Fe(III)content,producing Fe3O4 and FeOOH,which roughened the ZVI surfaces and formed dense agglomerates via crystal expansion,causing chemical clogging by occupying pore space.Overall,enhancing the electron selectivity and surface hydrophobicity of ZVI using surface modification methods can enhance its anti-clogging performance.展开更多
Recently,using anaerobic hydrolysis of waste activated sludge (WAS) to recover volatile fatty acids (VFAs) as carbon sources for denitrification has been widely studied,and the key is to solve the problem of improving...Recently,using anaerobic hydrolysis of waste activated sludge (WAS) to recover volatile fatty acids (VFAs) as carbon sources for denitrification has been widely studied,and the key is to solve the problem of improving the solubility and bioavailability of WAS organic matter.Considering the energy consumption and chemical cost,this paper used low-dose nanozero-valent iron (NZVI) coupled with low-intensity ultrasonication (US) to pretreat WAS,and explored the effects of different treatment sequences on the fragmentation of WAS flocs particles,the dissolution of organic matter,and the subsequent biofermentation conversion process.The results showed low-dose NZVI synchronized with low-intensity US (NZVIUS)worked best for WAS anaerobic fermentation.Compared with 2062 mg/L in control group,soluble chemical oxygen demand (SCOD) after NZVIUS treatment reached up to 2786 mg/L during the fermentation cycle,and the initial release rate of SCOD increased by 69%.The VFAs production was elevated from 1522 to 1940 mg COD/L.NZVIUS pretreatment promoted the solubilization of attached organic matter,manifested by the fragmentation of WAS flocs and cell lysis.At the same time,proteins and carbohydrates in the extracellular polymeric substances (EPS) had different types of migration and transformation,and transfer of EPS can contribute 35.6% to SCOD.Moreover,adding NZVI promoted PO_(4)^(3-)-P recovery in the fermentation supernatant by 22.3% more than in day 4 control.This study demonstrated that the NZVIUS pretreatment method can effectively improve the production of VFAs by WAS anaerobic fermentation,meeting the practical needs of wastewater plants.展开更多
Nano zero-valent iron(nZVI)is widely used in soil remediation due to its high reactivity.However,the easy agglomeration,poor antioxidant ability and passivation layer of Fe-Cr coprecipitates of nZVI have limited its a...Nano zero-valent iron(nZVI)is widely used in soil remediation due to its high reactivity.However,the easy agglomeration,poor antioxidant ability and passivation layer of Fe-Cr coprecipitates of nZVI have limited its application scale in Cr-contaminated soil remediation,especially in high concentration of Cr-contaminated soil.Herein,we found that the carboxymethyl cellulose on nZVI particles could increase the zeta potential value of soil and change the phase of nZVI.Along with the presence of biochar,97.0%and 96.6%Cr immobilization efficiency through CMC-nZVI/BC were respectively achieved in high and low concentrations of Cr-contaminated soils after 90-days remediation.In addition,the immobilization efficiency of Cr(VI)only decreased by 5.1%through CMC-nZVI/BC treatment after 10 weeks aging in air,attributing to the strong antioxidation ability.As for the surrounding Crcontaminated groundwater,the Cr(VI)removal capacity of CMC-nZVI/BC was evaluated under different reaction conditions through column experiments and COMSOL Multiphysics.CMC-nZVI/BC could efficiently remove 85%of Cr(VI)in about 400 hr when the initial Cr(VI)concentration was 40 mg/L and the flow rate was 0.5 mL/min.This study demonstrates that uniformly dispersed CMC-nZVI/BC has an excellent remediation effect on different concentrations of Cr-contaminated soils.展开更多
Graphene Oxide(GO),nanoscale Zero-Valent Iron(nZVI)and GO-modified nZVI(GO-nZVI)composite materials were prepared by the Hummer and polyphenol reduction method,respectively,and Scanning Electron Microscope(SEM)and X-r...Graphene Oxide(GO),nanoscale Zero-Valent Iron(nZVI)and GO-modified nZVI(GO-nZVI)composite materials were prepared by the Hummer and polyphenol reduction method,respectively,and Scanning Electron Microscope(SEM)and X-ray Diffraction(XRD)were used to characterize the morphology and phase composition of these materials.A series of batch experiments were then conducted to inves-tigate the performance and influencing factors of GO-nZVI activating peroxydisulfate(SPS)for the degra-dation of 1,2,3-trichloropropane(TCP).Finally,an in-situ oxidation reaction zone was created by GO-nZVI-activated SPS in a one-dimensional simulated system to study the remediation of TCP contamination under different aquifer conditions.The results showed that the GO-nZVI composite exhibited a porous,fluffy structure,with spherical nZVI particles loaded onto the surface and folds of the GO sheets.Compared with unmodified nZVI particles,the GO-nZVI composite significantly enhanced the removal efficiency of TCP by activated SPS,achieving a removal rate of 67.2%within an hour-78.2%higher than that of the unmodi-fied system.The SPS dosage and the C/Fe ratio in GO-nZVI were found to significantly affect the degradation efficiency of TCP.The removal rate of TCP increased with higher SPS concentration,and a 10%carbon addition,yielded the best activation effect.The one-dimensional simulation results indicated that the removal rate of TCP ranged from 30.1%to 73.3%under different conditions.A larger medium particle size and higher concentrations of reactants(SPS and GO-nZVI)improved pollutant degradation efficiency,increasing TCP removal by 62.1%,23.8%,and 3.7%,respectively.In contrast,a higher groundwater flow velocity was not conducive to the removal of pollutants,with the TCP removal rate decreasing by approxi-mately 41.9%.展开更多
Sulfamethoxazole(SMX)contamination in farmland disrupts soil micro-ecological functions,posing a risk to soil health and productivity.Sulfidated zero-valent iron(SZVI),a promising green material known for its good rea...Sulfamethoxazole(SMX)contamination in farmland disrupts soil micro-ecological functions,posing a risk to soil health and productivity.Sulfidated zero-valent iron(SZVI),a promising green material known for its good reactivity,had been used for soil remediation.However,existing studies often overlooked the effects of particle size and sulfur content on the long-term performance of SZVI and its impact on soil micro-ecological safety.This study employed polysulfide-modified nano,micro-nano,and micron-sized SZVI to investigate how particle size and sulfur content influenced the reactivity and durability,as well as the iron oxide forms and microbial community of soil during the SMX remediation.The results demonstrated that micro-nano sized SZVI(nm-SZVI)exhibited prolonged reactivity,achieving 83.12%-99.91%SMX removal over 30 days and maintaining higher levels of soil amorphous and reactive ferrous iron.Although sulfidation improved reactivity,excessive sulfur content reduced removal efficiency and accelerated the conversion to soil crystalline iron forms.Compared to nanoparticles,nm-SZVI fostered microbial diversity and balanced functional bacteria for electron transfer,organic matter utilization,and nutrient cycling.However,the elevated sulfur content in SZVI inhibited the stability of the microbial network.Finally,it was found that SMX underwent isoxazole reduction cleavage and oxidative removal pathways,reducing ecological toxicity.This study provided a new insight into the rational design of SZVI to achieve long-term pollutant removal and ensuring the health and stability of the microbial community by regulating particle size and sulfur content in soil remediation.展开更多
The MXenes,a new class of two-dimensional layered materials,have found extensive applications in water treatment for its excellent thermal stability,electrical conductivity,and excellent adsorption ability.Sulfidized ...The MXenes,a new class of two-dimensional layered materials,have found extensive applications in water treatment for its excellent thermal stability,electrical conductivity,and excellent adsorption ability.Sulfidized nano zero-valent iron(S-nZVI)is a good reducing agent,however,the practical application of S-nZVI is currently restricted due to the tendency of nano materials to agglomerate.Herein,MXenes use as a support and in situ loading S-nZVI on it to prepare a new material(S-nZVI/Ti_(3)C_(2)T_(x)),and applied it to U(VI)removal in water treatment.The microscopic characterization proves that S-nZVI on Ti_(3)C_(2)T_(x) has good dispersion and effectively alleviates agglomeration.Batch experiments shown that SnZVI/Ti_(3)C_(2)T_(x) has a very good effect on U(VI)removal,and themaximumadsorption capacity reaches 674.4mg/g under the aerobic condition at pH=6.0.The pseudo-second-order kinetic model and the Langmuir isotherm model were found to be more appropriate for describing the adsorption behavior.This indicates that the removal process is a single molecular layer chemisorption.Moreover,the S-nZVI/Ti_(3)C_(2)T_(x) maintained a removal efficiency of over 85%for U(VI)even after being reused five times,demonstrating its excellent reusability.It is worth noting that the material can remove 79.8%of 50 mg/L of U(VI)in simulated seawater,indicating that S-nZVI/Ti_(3)C_(2)T_(x) possessed an excellent uranium extraction performance from seawater.Experimental results and XPS analysis showed that U(VI)was removed by adsorption,reduction and co-precipitation.Moreover,S-nZVI/Ti_(3)C_(2)T_(x) was a lowtoxicitymaterial to Hyriopsis cumingii.Therefore,S-nZVI/Ti_(3)C_(2)T_(x) was expected to be a candidate as adsorbent with great potential in removal of uranium from wastewater and seawater.展开更多
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 s...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.展开更多
Nitrobenzene has been considered as a significant groundwater contaminant due to its wide usage in explosives, insecticides, herbicides, pharmaceuticals and dyes. Nitrobenzene is of environmental concern because of it...Nitrobenzene has been considered as a significant groundwater contaminant due to its wide usage in explosives, insecticides, herbicides, pharmaceuticals and dyes. Nitrobenzene is of environmental concern because of its toxicity. In the presence of zero-valent iron （ZVI）, reduction of the nitro group is the dominant transformation process for nitrobenzene. A series of experiments were carried out to investigate the kinetics of nitrobenzene reduction by ZVI and the effects of pH and ZVI particle size on nitrobenzene removal in groundwater. The results indicated that nitrobenzene could be reduced to aniline by ZVI; the reduction of nitrobenzene by ZVI followed a pseudo first-order kinetics; the observed nitrobenzene reduction rate constant （k obs ） was 0.0006 min^-1 and the half-life of nitrobenzene （t 1/2 ） was 115.5 min; the mass balance achieved 87.5% for nitrobenzene reduction by the 1 mm ZVI particle and the final removal efficiency was 80.98%. In addition, the pH and ZVI particle size were found to exhibit significant influences on the nitrobenzene reduction. The observed nitrobenzene reduction rate constant linearly decreased with increase pH and the data fitted on polynomial regression equation for the observed nitrobenzene reduction rate constant and ZVI particle size. Therefore, use of ZVI based permeable reactive barrier technology to remedy nitrobenzene contaminated groundwater was feasible.展开更多
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 ...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.展开更多
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...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.展开更多
Some problems including low treatment capacity,agglomeration and clogging phenomena,and short working life,limit the application of pre-treatment methods involving zero-valent iron （ZVI）.In this article,ZVI was froz...Some problems including low treatment capacity,agglomeration and clogging phenomena,and short working life,limit the application of pre-treatment methods involving zero-valent iron （ZVI）.In this article,ZVI was frozen in an amorphous state through a melt-spinning technique,and the decolorization effect of amorphous ZVI on Acid Orange II solution was investigated under varied conditions of experimental variables such as reaction temperature,ribbon dosage,and initial pH.Batch experiments suggested that the decolorization rate was enhanced with the increase of reaction temperature and ribbon dosage,but decreased with increasing initial solution pH.Kinetic analyses indicated that the decolorization process followed a first order exponential kinetic model,and the surface-normalized decolorization rate could reach 2.09 L/（m^2 ·min） at room temperature,which was about ten times larger than any previously reported under similar conditions.Recycling experiments also proved that the ribbons could be reused at least four times without obvious decay of decolorization rate and efficiency.This study suggests a tremendous application potential for amorphous ZVI in remediation of groundwater or wastewater contaminated with azo dyes.展开更多
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 nanosca...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.展开更多
Zero-valent iron amended biochar(ZVIB)has been proposed as a promising material in immobilizing heavy metals in paddy fields.In this study,the impacts of p H of ZVIB(p H 6.3 and p H 9.7)and watering management techniq...Zero-valent iron amended biochar(ZVIB)has been proposed as a promising material in immobilizing heavy metals in paddy fields.In this study,the impacts of p H of ZVIB(p H 6.3 and p H 9.7)and watering management techniques(watering amount in the order of CON(control,5/72)>3/72>1-3/72>3/100>1/72,with 5/72,for example,representing irrigation given to 5 cm above soil surface in 72 hr regular interval)on As and Cd bioavailability for rice and its grain yield(Yield BR)were investigated in a pot experiment.Brown rice As(As BR)content was irrelative to the watering treatments,while significantly decreased(>50%)with the addition of both ZVIB materials.The diminutions of brown rice Cd(Cd BR)content as well as the Yield BR were highly dependent on both the soil amendment materials’p H and watering amount.Among all the watering treatments,3/72 treatment(15%less irrigation water than the CON)with ZVIB 6.3 amendment was the optimum fit for simultaneous reduction of As BR(50%)and Cd BR contents(19%)as well as for significant increment(12%)of the Yield BR.Although high pH(9.7)ZVIB application could also efficiently decrease As and Cd contents in brown rice,it might risk grain yield lost if appropriate(e.g.3/72 in our study)watering management technique was not chosen.Therefore,ZVIB would be an environmentally friendly option as an amendment material with proper selection of watering management technique to utilize As and Cd co-contaminated arable soils safely for paddy cultivation.展开更多
Zero-valent iron（ZⅥ） was loaded on expanded graphite（EG） to produce a composite material（EG-ZⅥ） for efficient removal of hexavalent chromium（Cr（Ⅵ））. EG and EG-ZⅥ were characterized by X-ray diffraction（...Zero-valent iron（ZⅥ） was loaded on expanded graphite（EG） to produce a composite material（EG-ZⅥ） for efficient removal of hexavalent chromium（Cr（Ⅵ））. EG and EG-ZⅥ were characterized by X-ray diffraction（XRD）, scanning electron microscopy（SEM）,Fourier-transform infrared（FTIR） spectroscopy and Brunauer–Emmett–Teller（BET） analysis. EG-ZⅥ had a high specific surface area and contained sub-micron sized particles of zero-valent iron. Batch experiments were employed to evaluate the Cr（Ⅵ） removal performance. The results showed that the Cr（Ⅵ） removal rate was 98.80% for EG-ZⅥ,which was higher than that for both EG（10.00%） and ZⅥ（29.80%）. Furthermore, the removal rate of Cr（Ⅵ） by EG-ZⅥ showed little dependence on solution p H within a p H range of 1–9.Even at pH 11, a Cr（Ⅵ） removal rate of 62.44% was obtained after reaction for 1 hr. EG-ZⅥ could enhance the removal of Cr（Ⅵ） via chemical reduction and physical adsorption,respectively. X-ray photoelectron spectroscopy（XPS） was used to analyze the mechanisms of Cr（Ⅵ） removal, which indicated that the ZⅥ loaded on the surface was oxidized, and the removed Cr（Ⅵ） was immobilized via the formation of Cr（III） hydroxide and Cr（III）–Fe（III）hydroxide/oxyhydroxide on the surface of EG-ZⅥ.展开更多
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 pho...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.展开更多
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 contaminant...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 Fe S, 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 p H 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.展开更多
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 oxid...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 m^2/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.展开更多
Ligands may increase the yields of reactive oxygen species(ROS)in zero-valent iron(ZVI)/O2 systems.To clarify the relationship between the properties of ligands and their effects on the oxidative removal of contaminan...Ligands may increase the yields of reactive oxygen species(ROS)in zero-valent iron(ZVI)/O2 systems.To clarify the relationship between the properties of ligands and their effects on the oxidative removal of contaminants,five common ligands(formate,acetate,oxalate,ethylenediaminetetraacetic acid(EDTA),and phosphate)as well as acetylacetone(AA)were investigated with arsenite(As(III))as the target contaminant at three initial p H values(3.0,5.0,and 7.0).The addition of these ligands to the ZVI/O2 system resulted in quite different effects on As(III)removal.EDTA enhanced the oxidation of As(III)to arsenate(As(V))but inhibited the removal of As(V).Oxalate was the only ligand in this work that accelerated both the removal of As(III)and As(V).By analyzing the ligand effects from the four aspects:dissolution of surface iron(hydr)oxides,corrosion of ZVI,reaction with ROS,and interference with precipitation,the following properties of ligands were believed to be important:ability to provide dissociable protons,complexation ability with iron,and reactivity with ROS.The complexation ability is a double-edged sword.It could enhance the generation of ROS by reducing the reduction potential of the Fe(III)/Fe(II)redox couple,but also could inhibit the removal of arsenic by coprecipitation.The elucidated relationship between the key property parameters of ligands and their effects on the ZVI/O2 system is helpful for the rational design of effective ZVI/ligand/O2 systems.展开更多
基金supported by the National Natural Science Foundation of China(No.21777139)the National Key Research and Development Program of China(No.2017YFA0207003).
文摘The earthworm-based vermiremediation facilitated with benign chemicals such as nano zero-valent iron(nZVI)is a promising approach for the remediation of a variety of soil contaminants including cyanotoxins.As themost toxic cyanotoxin,microcystin-LR(MC-LR)enter soil via runoff,irrigated surface water and sewage,and the application of cyanobacterial biofertilizers as part of the sustainable agricultural practice.Earthworms in such remediation systems must sustain the potential risk from both nZVI and MC-LR.In the present study,earthworms(Eisenia fetida)were exposed up to 14 days to MC-LR and nZVI(individually and inmixture),and the toxicity was investigated at both the organismal andmetabolic levels,including growth,tissue damage,oxidative stress,metabolic response and gut microbiota.Results showed that co-exposure of MC-LR and nZVI is less potent to earthworms than that of separate exposure.Histological observations in the co-exposure group revealed only minor epidermal brokenness,and KEGG enrichment analysis showed that co-exposure induced earthworms to regulate glutathione biosynthesis for detoxification and reduced adverse effects from MC-LR.The combined use of nZVI promoted the growth and reproduction of soil and earthworm gut bacteria(e.g.,Sphingobacterium and Acinetobacter)responsible for the degradation of MC-LR,whichmight explain the observed antagonism between nZVI and MC-LR in earthworm microcosm.Our study suggests the beneficial use of nZVI to detoxify pollutants in earthworm-based vermiremediation systems where freshwater containing cyanobacterial blooms is frequently used to irrigate soil and supply water for the growth and metabolism of earthworms.
基金financially supported by the National Natural Science Foundation of China(Nos.42030702,42307014,and 42077354)the Guangdong Foundation for Program of Science and Technology Research(No.2020B1212060048)+7 种基金the China Postdoctoral Science Foundation(No.2022M720847)the GDAS’Project of Science and Technology Development(Nos.2023GDASZH-2023010103,and 2020GDASYL-20200104017)the open competition program of top ten critical priorities of Agricultural Science and Technology Innovation for the 14th Five-Year Plan of Guangdong Province(No.2022SDZG08)Research Project of Hunan Provincial Department of Education(No.21C0788)National Key Technology R&D Program of China(No.2022YFD1700804)Guangdong Province Key Field R&D Project(No.2023B0202010027)Guangzhou Science and Technology Plan Project(No.2023B03J1286)the research platformwas also supported by Guangdong Science and Technology Infrastructure development(No.2019B121201004).
文摘Antimony(Sb)contamination in paddy fields can lead to its accumulation in rice grains,posing a threat to food safety.To address this issue,the combined use of zero-valent iron(ZVI)and biochar(BC)were applied to decrease the uptake of Sb in Sb-polluted soils,and their effects on Sb uptake from soil to rice grains were investigated.Our results showed that the combination treatment of 0.05%ZVI and 0.095%BC resulted in a significant decrease(42.8%)in Sb accumulation in rice grains that was comparably more efficient than that by 0.05%ZVI(decrease of 15.8%Sb accumulation)or 0.095%BC(decrease of 12.7%Sb accumulation)alone,demonstrating the synergistic effect of ZVI and BC on mitigating Sb uptake by rice plants.ZVI presence resulted in the formation of iron oxides in the soil and on root surfaces,and the S^(2-)/S_(2)^(2-)ascent also increased by 58.7%on day 75 compared with that of the control,facilitating the reduction of Sb(Ⅴ)to less mobile Sb(Ⅲ),thereby decreasing Sb accumulation in rice plants.BC initially increased themobility of Sb owing to its alkaline nature,whereas the electron shuttle properties of BC contributed to a decrease in Sbmobility.The abundance of the arsenite-reducing gene arrA ultimately increased by 203.2% on day 120 compared with the initial phase on day 5,and BC caused a remarkable increase in arrA gene abundance.This study revealed the synergistic mechanisms by combining ZVI and BC to mitigate Sb uptake by rice,which may be useful for the sustainable remediation of contaminated rice paddies.
基金supported by Chinese Research Academy of Environmental Sciences(No.2024YSKY-44)the National Key R&D Program of China(No.2023YFC3708003).
文摘Clogging of zero-valent iron(ZVI)is among the most prominent technical bottlenecks limiting its application in long-term groundwater remediation.In this study,three ZVI species with different oxygenated anion modifications on the surface—micron ZVI(mZVI),oxalated mZVI(OX-mZVI),and phosphorylated mZVI(P-mZVI)—were selected to conduct a comparative study on the clogging problem during remediation of nitrobenzene-contaminated groundwater.The clogging degree(ΦC)was innovatively employed to quantify ZVI clogging,and the clogging mechanisms of influencing factors were uncovered by analyzing changes inΦC,reactivity,volume expansion,iron valence state,and iron corrosion product(FeCP)species.Results revealed that the clogging resistance of ZVI decreased in the following order:P-mZVI>OX-mZVI>mZVI.The reduction process of nitrobenzene controlled the increase ofΦC,and the reduction of NO_(3)^(−)—a groundwater background ion—served as an indicator for clogging stage changes.Surface chemistry analysis revealed that the increase ofΦC originated from the volume expansion effect of FeCPs.Iron corrosion increased the Fe(III)content,producing Fe3O4 and FeOOH,which roughened the ZVI surfaces and formed dense agglomerates via crystal expansion,causing chemical clogging by occupying pore space.Overall,enhancing the electron selectivity and surface hydrophobicity of ZVI using surface modification methods can enhance its anti-clogging performance.
基金supported by Sichuan Environmental Protection Industry Group Co.,Ltd.,China(No.2021-CNSW-A01).
文摘Recently,using anaerobic hydrolysis of waste activated sludge (WAS) to recover volatile fatty acids (VFAs) as carbon sources for denitrification has been widely studied,and the key is to solve the problem of improving the solubility and bioavailability of WAS organic matter.Considering the energy consumption and chemical cost,this paper used low-dose nanozero-valent iron (NZVI) coupled with low-intensity ultrasonication (US) to pretreat WAS,and explored the effects of different treatment sequences on the fragmentation of WAS flocs particles,the dissolution of organic matter,and the subsequent biofermentation conversion process.The results showed low-dose NZVI synchronized with low-intensity US (NZVIUS)worked best for WAS anaerobic fermentation.Compared with 2062 mg/L in control group,soluble chemical oxygen demand (SCOD) after NZVIUS treatment reached up to 2786 mg/L during the fermentation cycle,and the initial release rate of SCOD increased by 69%.The VFAs production was elevated from 1522 to 1940 mg COD/L.NZVIUS pretreatment promoted the solubilization of attached organic matter,manifested by the fragmentation of WAS flocs and cell lysis.At the same time,proteins and carbohydrates in the extracellular polymeric substances (EPS) had different types of migration and transformation,and transfer of EPS can contribute 35.6% to SCOD.Moreover,adding NZVI promoted PO_(4)^(3-)-P recovery in the fermentation supernatant by 22.3% more than in day 4 control.This study demonstrated that the NZVIUS pretreatment method can effectively improve the production of VFAs by WAS anaerobic fermentation,meeting the practical needs of wastewater plants.
基金supported by the National Key Research and Development Program of China(No.2020YFC1808701)the Fundamental Research Funds for the Central Universities(No.buctrc202232).
文摘Nano zero-valent iron(nZVI)is widely used in soil remediation due to its high reactivity.However,the easy agglomeration,poor antioxidant ability and passivation layer of Fe-Cr coprecipitates of nZVI have limited its application scale in Cr-contaminated soil remediation,especially in high concentration of Cr-contaminated soil.Herein,we found that the carboxymethyl cellulose on nZVI particles could increase the zeta potential value of soil and change the phase of nZVI.Along with the presence of biochar,97.0%and 96.6%Cr immobilization efficiency through CMC-nZVI/BC were respectively achieved in high and low concentrations of Cr-contaminated soils after 90-days remediation.In addition,the immobilization efficiency of Cr(VI)only decreased by 5.1%through CMC-nZVI/BC treatment after 10 weeks aging in air,attributing to the strong antioxidation ability.As for the surrounding Crcontaminated groundwater,the Cr(VI)removal capacity of CMC-nZVI/BC was evaluated under different reaction conditions through column experiments and COMSOL Multiphysics.CMC-nZVI/BC could efficiently remove 85%of Cr(VI)in about 400 hr when the initial Cr(VI)concentration was 40 mg/L and the flow rate was 0.5 mL/min.This study demonstrates that uniformly dispersed CMC-nZVI/BC has an excellent remediation effect on different concentrations of Cr-contaminated soils.
基金financially supported by the Basal Research Fund of Chinese Academy of Geological Sciences(NO.SK202318)the Natural Science Foundation of Xiamen,China(No.3502Z20227309)the Natural Science Foundation of Fujian Province of China(NO.2023J01227).
文摘Graphene Oxide(GO),nanoscale Zero-Valent Iron(nZVI)and GO-modified nZVI(GO-nZVI)composite materials were prepared by the Hummer and polyphenol reduction method,respectively,and Scanning Electron Microscope(SEM)and X-ray Diffraction(XRD)were used to characterize the morphology and phase composition of these materials.A series of batch experiments were then conducted to inves-tigate the performance and influencing factors of GO-nZVI activating peroxydisulfate(SPS)for the degra-dation of 1,2,3-trichloropropane(TCP).Finally,an in-situ oxidation reaction zone was created by GO-nZVI-activated SPS in a one-dimensional simulated system to study the remediation of TCP contamination under different aquifer conditions.The results showed that the GO-nZVI composite exhibited a porous,fluffy structure,with spherical nZVI particles loaded onto the surface and folds of the GO sheets.Compared with unmodified nZVI particles,the GO-nZVI composite significantly enhanced the removal efficiency of TCP by activated SPS,achieving a removal rate of 67.2%within an hour-78.2%higher than that of the unmodi-fied system.The SPS dosage and the C/Fe ratio in GO-nZVI were found to significantly affect the degradation efficiency of TCP.The removal rate of TCP increased with higher SPS concentration,and a 10%carbon addition,yielded the best activation effect.The one-dimensional simulation results indicated that the removal rate of TCP ranged from 30.1%to 73.3%under different conditions.A larger medium particle size and higher concentrations of reactants(SPS and GO-nZVI)improved pollutant degradation efficiency,increasing TCP removal by 62.1%,23.8%,and 3.7%,respectively.In contrast,a higher groundwater flow velocity was not conducive to the removal of pollutants,with the TCP removal rate decreasing by approxi-mately 41.9%.
基金supported by the National Natural Science Foundation of China(No.22478226)Shandong Provincial Natural Science Foundation(Nos.ZR2023JQ022 and ZR2024QE165)+1 种基金the Postdoctoral Fellowship Program of CPSF(No.GZC20240917)Taishan Scholars Project of Shandong Province(No.tstp20230604)。
文摘Sulfamethoxazole(SMX)contamination in farmland disrupts soil micro-ecological functions,posing a risk to soil health and productivity.Sulfidated zero-valent iron(SZVI),a promising green material known for its good reactivity,had been used for soil remediation.However,existing studies often overlooked the effects of particle size and sulfur content on the long-term performance of SZVI and its impact on soil micro-ecological safety.This study employed polysulfide-modified nano,micro-nano,and micron-sized SZVI to investigate how particle size and sulfur content influenced the reactivity and durability,as well as the iron oxide forms and microbial community of soil during the SMX remediation.The results demonstrated that micro-nano sized SZVI(nm-SZVI)exhibited prolonged reactivity,achieving 83.12%-99.91%SMX removal over 30 days and maintaining higher levels of soil amorphous and reactive ferrous iron.Although sulfidation improved reactivity,excessive sulfur content reduced removal efficiency and accelerated the conversion to soil crystalline iron forms.Compared to nanoparticles,nm-SZVI fostered microbial diversity and balanced functional bacteria for electron transfer,organic matter utilization,and nutrient cycling.However,the elevated sulfur content in SZVI inhibited the stability of the microbial network.Finally,it was found that SMX underwent isoxazole reduction cleavage and oxidative removal pathways,reducing ecological toxicity.This study provided a new insight into the rational design of SZVI to achieve long-term pollutant removal and ensuring the health and stability of the microbial community by regulating particle size and sulfur content in soil remediation.
基金supported by the National Natural Science Foundation of China(No.42277063)the Postdoctoral Research Foundation of China(No.2021M702886)+1 种基金the Leading Innovative Talents cultivation Project of Changzhou City(No.CQ20230096)the Research Initiation Project of Changzhou University.
文摘The MXenes,a new class of two-dimensional layered materials,have found extensive applications in water treatment for its excellent thermal stability,electrical conductivity,and excellent adsorption ability.Sulfidized nano zero-valent iron(S-nZVI)is a good reducing agent,however,the practical application of S-nZVI is currently restricted due to the tendency of nano materials to agglomerate.Herein,MXenes use as a support and in situ loading S-nZVI on it to prepare a new material(S-nZVI/Ti_(3)C_(2)T_(x)),and applied it to U(VI)removal in water treatment.The microscopic characterization proves that S-nZVI on Ti_(3)C_(2)T_(x) has good dispersion and effectively alleviates agglomeration.Batch experiments shown that SnZVI/Ti_(3)C_(2)T_(x) has a very good effect on U(VI)removal,and themaximumadsorption capacity reaches 674.4mg/g under the aerobic condition at pH=6.0.The pseudo-second-order kinetic model and the Langmuir isotherm model were found to be more appropriate for describing the adsorption behavior.This indicates that the removal process is a single molecular layer chemisorption.Moreover,the S-nZVI/Ti_(3)C_(2)T_(x) maintained a removal efficiency of over 85%for U(VI)even after being reused five times,demonstrating its excellent reusability.It is worth noting that the material can remove 79.8%of 50 mg/L of U(VI)in simulated seawater,indicating that S-nZVI/Ti_(3)C_(2)T_(x) possessed an excellent uranium extraction performance from seawater.Experimental results and XPS analysis showed that U(VI)was removed by adsorption,reduction and co-precipitation.Moreover,S-nZVI/Ti_(3)C_(2)T_(x) was a lowtoxicitymaterial to Hyriopsis cumingii.Therefore,S-nZVI/Ti_(3)C_(2)T_(x) was expected to be a candidate as adsorbent with great potential in removal of uranium from wastewater and seawater.
基金financially supported by the National Natural Science Foundation of China(2187616141420104007)+3 种基金the National Key Research and Development Project of China(No.2018YFF0213403)Guangdong Academy of Sciences’Project(2019GDASYL-01020062019GDASYL-03010022018GDASCX-0501)。
文摘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.
基金supported by the National High Technology Research and Development Program(863) of China(No.2007AA06A410)the Water Pollution Control and Management Project(No.2008ZX07207-007-05)the National Natural Science Foundation of China(No.40802055)
文摘Nitrobenzene has been considered as a significant groundwater contaminant due to its wide usage in explosives, insecticides, herbicides, pharmaceuticals and dyes. Nitrobenzene is of environmental concern because of its toxicity. In the presence of zero-valent iron （ZVI）, reduction of the nitro group is the dominant transformation process for nitrobenzene. A series of experiments were carried out to investigate the kinetics of nitrobenzene reduction by ZVI and the effects of pH and ZVI particle size on nitrobenzene removal in groundwater. The results indicated that nitrobenzene could be reduced to aniline by ZVI; the reduction of nitrobenzene by ZVI followed a pseudo first-order kinetics; the observed nitrobenzene reduction rate constant （k obs ） was 0.0006 min^-1 and the half-life of nitrobenzene （t 1/2 ） was 115.5 min; the mass balance achieved 87.5% for nitrobenzene reduction by the 1 mm ZVI particle and the final removal efficiency was 80.98%. In addition, the pH and ZVI particle size were found to exhibit significant influences on the nitrobenzene reduction. The observed nitrobenzene reduction rate constant linearly decreased with increase pH and the data fitted on polynomial regression equation for the observed nitrobenzene reduction rate constant and ZVI particle size. Therefore, use of ZVI based permeable reactive barrier technology to remedy nitrobenzene contaminated groundwater was feasible.
基金supported by grants from Tai Shan Scholar Foundation(No.ts 201511003)
文摘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.
基金support provided by the National Key Technology R&D Program(no.2012BAJ21B04)the financial support from the China Scholarship Council(CSC)for one year as a visiting scholar at Stevens Institute of Technology
文摘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.
基金the financial support from the Ministry of Science and Technology of China(No. 2011CB606301)the National Natural Science Foundation of China (No. 50825402,51101156)
文摘Some problems including low treatment capacity,agglomeration and clogging phenomena,and short working life,limit the application of pre-treatment methods involving zero-valent iron （ZVI）.In this article,ZVI was frozen in an amorphous state through a melt-spinning technique,and the decolorization effect of amorphous ZVI on Acid Orange II solution was investigated under varied conditions of experimental variables such as reaction temperature,ribbon dosage,and initial pH.Batch experiments suggested that the decolorization rate was enhanced with the increase of reaction temperature and ribbon dosage,but decreased with increasing initial solution pH.Kinetic analyses indicated that the decolorization process followed a first order exponential kinetic model,and the surface-normalized decolorization rate could reach 2.09 L/（m^2 ·min） at room temperature,which was about ten times larger than any previously reported under similar conditions.Recycling experiments also proved that the ribbons could be reused at least four times without obvious decay of decolorization rate and efficiency.This study suggests a tremendous application potential for amorphous ZVI in remediation of groundwater or wastewater contaminated with azo dyes.
基金supported by the National Basic Research and Development Program (973) of China (No. 2007CB936604)
文摘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.
基金the National Key Research and Development Program of China(No.2017YFD0801003)。
文摘Zero-valent iron amended biochar(ZVIB)has been proposed as a promising material in immobilizing heavy metals in paddy fields.In this study,the impacts of p H of ZVIB(p H 6.3 and p H 9.7)and watering management techniques(watering amount in the order of CON(control,5/72)>3/72>1-3/72>3/100>1/72,with 5/72,for example,representing irrigation given to 5 cm above soil surface in 72 hr regular interval)on As and Cd bioavailability for rice and its grain yield(Yield BR)were investigated in a pot experiment.Brown rice As(As BR)content was irrelative to the watering treatments,while significantly decreased(>50%)with the addition of both ZVIB materials.The diminutions of brown rice Cd(Cd BR)content as well as the Yield BR were highly dependent on both the soil amendment materials’p H and watering amount.Among all the watering treatments,3/72 treatment(15%less irrigation water than the CON)with ZVIB 6.3 amendment was the optimum fit for simultaneous reduction of As BR(50%)and Cd BR contents(19%)as well as for significant increment(12%)of the Yield BR.Although high pH(9.7)ZVIB application could also efficiently decrease As and Cd contents in brown rice,it might risk grain yield lost if appropriate(e.g.3/72 in our study)watering management technique was not chosen.Therefore,ZVIB would be an environmentally friendly option as an amendment material with proper selection of watering management technique to utilize As and Cd co-contaminated arable soils safely for paddy cultivation.
基金supported by the National Key Research and Development Program of China(No.2017YFD0801503)the Fundamental Research Funds for the Central Universities(No.PYVZ1703)the Higher Education and High-quality and World-class Universities(PY201606)
文摘Zero-valent iron（ZⅥ） was loaded on expanded graphite（EG） to produce a composite material（EG-ZⅥ） for efficient removal of hexavalent chromium（Cr（Ⅵ））. EG and EG-ZⅥ were characterized by X-ray diffraction（XRD）, scanning electron microscopy（SEM）,Fourier-transform infrared（FTIR） spectroscopy and Brunauer–Emmett–Teller（BET） analysis. EG-ZⅥ had a high specific surface area and contained sub-micron sized particles of zero-valent iron. Batch experiments were employed to evaluate the Cr（Ⅵ） removal performance. The results showed that the Cr（Ⅵ） removal rate was 98.80% for EG-ZⅥ,which was higher than that for both EG（10.00%） and ZⅥ（29.80%）. Furthermore, the removal rate of Cr（Ⅵ） by EG-ZⅥ showed little dependence on solution p H within a p H range of 1–9.Even at pH 11, a Cr（Ⅵ） removal rate of 62.44% was obtained after reaction for 1 hr. EG-ZⅥ could enhance the removal of Cr（Ⅵ） via chemical reduction and physical adsorption,respectively. X-ray photoelectron spectroscopy（XPS） was used to analyze the mechanisms of Cr（Ⅵ） removal, which indicated that the ZⅥ loaded on the surface was oxidized, and the removed Cr（Ⅵ） was immobilized via the formation of Cr（III） hydroxide and Cr（III）–Fe（III）hydroxide/oxyhydroxide on the surface of EG-ZⅥ.
文摘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.
基金financially supported by the National Natural Science Foundation of China (No.51408101)the Key Research and Development (R&D) Program from the Department of Science and Technology of Sichuan Province (No.2018FZ0011).
文摘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 Fe S, 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 p H 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.
基金supported by the National Natural Science Foundation of China(Nos.51578398,and 21707104)the National Postdoctoral Program for Innovative Talents(No.BX201700172)the Fundamental Research Funds for the Central Universities(No.0400219376)
文摘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 m^2/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.
基金supported by the National Key Research and Development Program of China (No. 2018YFC1802003)the National Natural Science Foundation of China (No. 21677070)the Outstanding PhD candidates of Nanjing University (No. 201801B032)
文摘Ligands may increase the yields of reactive oxygen species(ROS)in zero-valent iron(ZVI)/O2 systems.To clarify the relationship between the properties of ligands and their effects on the oxidative removal of contaminants,five common ligands(formate,acetate,oxalate,ethylenediaminetetraacetic acid(EDTA),and phosphate)as well as acetylacetone(AA)were investigated with arsenite(As(III))as the target contaminant at three initial p H values(3.0,5.0,and 7.0).The addition of these ligands to the ZVI/O2 system resulted in quite different effects on As(III)removal.EDTA enhanced the oxidation of As(III)to arsenate(As(V))but inhibited the removal of As(V).Oxalate was the only ligand in this work that accelerated both the removal of As(III)and As(V).By analyzing the ligand effects from the four aspects:dissolution of surface iron(hydr)oxides,corrosion of ZVI,reaction with ROS,and interference with precipitation,the following properties of ligands were believed to be important:ability to provide dissociable protons,complexation ability with iron,and reactivity with ROS.The complexation ability is a double-edged sword.It could enhance the generation of ROS by reducing the reduction potential of the Fe(III)/Fe(II)redox couple,but also could inhibit the removal of arsenic by coprecipitation.The elucidated relationship between the key property parameters of ligands and their effects on the ZVI/O2 system is helpful for the rational design of effective ZVI/ligand/O2 systems.
