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.

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

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

nZVI强化活性污泥对偶氮染料脱色及对微生物产物的影响

为研究纳米零价铁(nano-scale zero-valent iron,nZVI)对活性污泥强化偶氮染料脱色及对活性污泥微生物产物的影响,采用间歇试验考察投加nZVI对厌氧/好氧处理偶氮染料活性艳红K-2BP的活性污泥系统中,污染物去除效果及微生物胞外聚合物(EPS)和溶解性微生物产物(SMP)的影响。结果表明,在投加nZVI的活性污泥系统中(R2),活性艳红K-2BP在12h内的脱色率达到97%,远高于未投加的活性污泥系统(28%)(R1)。nZVI的投加降低了R2厌氧段化学需氧量(COD)的降解速率,而在好氧段COD降解速率几乎不受影响。nZVI腐蚀生成的Fe2+降低了R2中EPS的提取量,同时nZVI投加和K-2BP降解中间产物刺激了SMP的产生,R2中厌氧末和好氧末SMP含量分别是R1的1.2和1.5倍。

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

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

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

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

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

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

Monodisperse amino-modified nanosized zero-valent iron for selective and recyclable removal of TNT: Synthesis, characterization, and removal mechanism

Nitroaromatic explosives are major pollutants produced during wars that cause serious environmental and health problems. The removal of a typical nitroaromatic explosive, 2,4,6-trinitrotoluene(TNT), from aqueous solution, was conducted using a new recyclable magnetic nano-adsorbent(Fe@SiO_(2) –NH_(2)). This adsorbent was prepared by grafting amino groups onto Fe@SiO_(2) particles with a well-defined core-shell structure and demonstrated monodispersity in solution. The removal performance of the nano-adsorbent towards TNT was found to be 2.57 and 4.92 times higher than that towards two analogous explosives, 2,4-dinitrotoluene(2,4-DNT) and 2-nitrotoluene(2-NT), respectively, under neutral conditions. The difference in the removal performance among the three compounds was further compared in terms of the effects of different conditions(pH value, ionic strength, humic acid concentration, adsorbent modification degree and dosage, etc.) and the electrostatic potential distributions of the three compounds. The most significant elevation is owing to modification of amino on Fe@SiO_(2) which made a 20.7% increase in adsorption efficiency of TNT. The experimental data were well fit by the pseudo-second-order kinetic model and the Freundlich adsorption isotherm model, indicating multilayer adsorption on a heterogeneous surface. The experimental results and theoretical considerations show that the interactions between Fe@SiO_(2) –NH_(2) NPs and TNT correspond to dipole-dipole and hydrophobic interactions. These interactions should be considered in the design of an adsorbent. Furthermore, the adaptability to aqueous environment and excellent regeneration capacity of Fe@SiO_(2) –NH_(2) NPs makes these remediation materials promising for applications.

An adsorption study of^99Tc using nanoscale zero-valent iron supported on D001 resin

Nanoscale zero-valent iron(nZVI)supported on D001 resin(D001-nZVI)was synthesized for adsorption of high solubility and mobility radionuclide^99Tc.Re(VII),a chemical substitute for^99Tc,was utilized in batch experiments to investigate the feasibility and adsorption mechanism toward Tc(VII).Factors(pH,resin dose)affecting Re(VII)adsorption were studied.The high adsorption efficiency of Re(VII)at pH=3 and the solid-liquid ratio of 20 g/L.X-ray diffraction patterns revealed the reduction of ReO^?4 into ReO2 immobilized in D001-nZVI.Based on the optimum conditions of Re(VII)adsorption,the removal experiments of Tc(VII)were conducted where the adsorption efficiency of Tc(VII)can reach 94%.Column experiments showed that the Thomas model gave a good fit to the adsorption process of Re(VII)and the maximum dynamic adsorption capacity was 0.2910 mg/g.

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

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

包覆型纳米零价铁的制备及其对染料溶液的脱色性能

采用一步法合成了SiO2覆型纳米零价铁（SiO2-NZVI），并采用TEM，XRD，FTIR及EDS方对其进行了表征，考察了SiO2-NZVI对偶氮、蒽醌、三苯甲烷3种不同类型的染料溶液的脱色能力。表征结果表明：SiO2-NZVI平均粒径为15-22nm，SiO，薄膜厚度均一，约为10nm；SiO2-NZVI中所含元素主要为Fe和Si，质量比为90．6：9．4。实验结果表明：SiO2-NZVI对3种染料溶液均具有脱色能力，在染料溶液质量浓度为100mg／L、SiO2-NZVI加入量为2g／L、反应时间为35min的条件下，对甲基橙、孔雀石绿、洋红溶液的脱色率分别为86．04％，97．50％，82．13％；SiO2-NZVI相对于NZVI有更强的抗氧化能力，且酸性环境有利于SiO2-NZVI对染料溶液的脱色。

CMC-nZVI对高硫矿山土壤中铜的固定效果及机理

纳米零价铁(Nanoscale zero-valent iron,n ZVI)因具有较大比表面积和较强还原能力,常被用于原位修复变价重金属污染土壤,而对其应用于高硫富铜矿山土壤的修复及机理研究却鲜见报道.本研究以羧甲基纤维素-纳米零价铁(CMC-n ZVI)为供试材料,以广东省大宝山矿区高硫富铜土壤为供试土壤,按水土比1 g∶5 m L将CMC-n ZVI与矿山土壤混合均匀,通过毒性淋溶提取、重金属形态和酸可挥发性硫化物提取等实验,探究了CMC-n ZVI对矿山土壤中Cu的固定效果及机制.结果表明:(1)CMC-n ZVI对高硫土壤中的Cu具有极好的固定效果,毒性淋溶提取实验结果表明,n ZVI处理土壤中Cu的浸出浓度低于15 mg·kg-1,达到安全标准;(2)n ZVI可促进厌氧微生物的活性,促进土壤中大量硫酸盐被还原,因此Cu可能被Fe S、Fe S2吸附或直接生成硫化物沉淀,最终固定于土壤中;(3)新生成的无定形或微晶型次级铁矿物易通过吸附或共沉淀将游离的Cu(II)固定.

纳米Fe^0粒子对产乙烯脱卤菌群脱氯性能和多样性影响研究

为探讨纳米Fe0粒子对产乙烯脱卤菌群脱氯性能和物种多样性的影响,采用纳米Fe0粒子与产乙烯脱卤菌群联合脱氯,并通过气相色谱、PCR-DGGE和TEM等技术手段进行相关表征.结果表明:当纳米Fe0粒子浓度为0~0.50 g·L-1时,体系的脱氯速率提高较小,低于40%,且菌种数量无明显变化;当其浓度为0.50~1.00 g·L-1时,体系的脱氯速率由0.31μmol·h-1提高到0.77μmol·h-1,体系的脱氯速率提高了60%,部分DGGE条带消失,多样性减少.TEM结果显示,产乙烯脱卤拟球菌在与纳米Fe0粒子接触部位有轻度破损,但细胞没有破裂.纳米Fe0粒子浓度较高时对产乙烯脱卤菌群的脱氯有明显的促进作用,但会使产乙烯脱卤菌群物种多样性减少.