High-level arsenite removal from groundwater by zero-valent iron

The objectives of this study were to conduct batch and column studies to (i) assess the effectiveness of zero-valent iron for arsenic remediation in groundwater, (ii) determine removal mechanisms of arsenic, and (iii) evaluate implications of these processes with regard to the stability of arsenic and long-term remedial performance of the permeable reactive barrier (PRB) technology. A high concentration arsenic solution (50 mg l(-1)) was prepared by using sodium arsenite (arsenic (III)) to simulate groundwater at a heavily contaminated Superfund site in the USA. Batch studies indicate that the removal of arsenic is a two-step reaction with fast initial disappearance of arsenite followed by a slow subsequent removal process. Flow-through columns were conducted at a flow rate of 17 ml h(-1) under reducing conditions for 6.6 mo. Kinetic analysis suggested that arsenic removal behaves as a zero-order reaction at high arsenic concentrations. Arsenic removal rate constants decreased with time and arsenic breakthrough was observed in the column study. Arsenic removal capacity of zero-valent iron was determined to be approximately 7.5 mg As/g Fe. Carbonate green rust was identified from the analysis of surface precipitates; arsenite uptake by green rust may be a major mechanism responsible for arsenic remediation by zero-valent iron. Analysis of HCl-extractable arsenic from iron samples indicated that approximately 28% of arsenic was in the form of arsenate suggesting that a surface oxidation process was involved in the arsenic removal with zero-valent iron.     

金属铁还原脱氯处理有机氯化物的研究进展

本文对金属铁在还原降解六氯乙烷、四氯化碳、氯仿、三氯乙烯、四氯乙烯、二氯乙烯、氯乙烯、五氯酚、多氯联苯等有机氯化物中的应用作了评述 ,讨论了金属铁降解有机氯化物的反应机理及动力学。     

Rapid removal of flutriafol in water by zero-valent iron powder

A study of the effect of zero-valent iron (ZVI) powder is carried out for the first time on the degradation of flutriafol ((RS)-2,4'-difluoro-alpha-(1H-1,2,4-triazol-1-ylmethyl)-benzhydryl alcohol, C(16)H(13)F(2)N(3)O), a bifluorinated soil and water persistent triazole pesticide using a laboratory scale device consisting of a 20 ml pyrex serum vials fixed to a Vortex agitator. Different amounts of ZVI powder (10-50 g l(-1)) at pH 6.6 and room temperature were investigated. Experiments showed an observed degradation rate k(obs) directly proportional to the surface of contact of flutriafol with ZVI. Flutriafol degradation reactions demonstrated first order kinetic with a half-live of about 10.8+/-0.5 min and 3.6+/-0.2 min when experiments were conducted at [ZVI]=10 g l(-1) into oxygenated and anoxic solutions, respectively. Three analytical techniques were employed to monitor flutriafol degradation and to understand solution and by-products behaviors: (1) A UV-Vis spectrophotometer; (2) a high performance liquid chromatography (HPLC) coupled with a photo diode array (PDA) and fluorescence detectors; (3) a similar HPLC coupled with a PDA and a mass spectrometer detectors equipped with an atmospheric pressure photoionization source. Results showed a complete disappearance of flutriafol after 20 min of contact with ZVI, the loss of fluorescence properties of the final by-products, the defluorination of the triazole pesticide via hydroxylation reaction and finally the hydrogenation of the triazole ring.     

纳米零价铁颗粒除磷反应机理

从溶液化学与固相表征两方面对纳米零价铁(NZVI)去除水中磷酸根(PO43-)的机理进行初步探究。分别研究不同初始pH值、溶解氧(DO)对NZVI除磷效果的影响,结果表明,酸性环境(pH为3.0~7.0)有利于NZVI除磷,且初始pH值越低,磷去除率越高;好氧环境较厌氧环境更利于磷的去除,DO>8.0 mg/L时对磷酸根的去除率是厌氧条件(DO2等7种不同去除材料中以Ca(OH)2的共沉淀作用去除率最大(99.9%),NZVI次之(87.2%),表明NZVI除磷机理中还存在共沉淀作用。采用多种固相表征手段对NZVI除磷前后进行分析:扫描电子显微镜(SEM)显示反应后出现不规则颗粒;X射线衍射(XRD)表明Fe3(PO4)2是主要反应产物;X射线光电子能谱(XPS)分析未发现磷被还原成低价态。研究表明,NZVI可有效去除水中磷酸根,主要去除机理包括:NZVI对磷酸根的吸附作用、NZVI在水中腐蚀产生的Fe2+离子对磷酸根的化学沉淀作用及铁氢氧化物与磷酸根的共沉淀作用。     

Using nanoscale zero-valent iron for the remediation of polycyclic aromatic hydrocarbons contaminated soil

The sites contaminated with recalcitrant organic compounds, such as polycyclic aromatic hydrocarbons (PAHs) with multiple benzene rings, are colossal and ubiquitous environmental problems. They are relatively nonbiodegradable and mutagenic, and 16 of them are listed in the U.S. Environment Protection Agency priority pollutants. Thus, the efficient and emerging remediation technologies for removal of PAHs in contaminated sites have to be uncovered urgently. In this decade, the zero-valent iron (ZVI) particles have been used successfully in the laboratory, pilot, and field, such as degradation of chlorinated hydrocarbons and remediation of the other pollutants. Nevertheless, as far as we know, little research has investigated for soil remediation; this study used nanoscale ZVI particles to remove pyrene in the soil. The experimental variables were determined, including reaction time, iron particle size, and dosage. From the results, both the micro- and nanoscales of ZVI were capable of removing the target compound in soil, but the higher removal efficiencies were by nanoscale ZVI because of the massive specific surface area. The optimal operating conditions to attain the best removal efficiency of pyrene were obtained while adding nanoscale ZVI 0.1 g/g soil within 60 min and 150 rpm of mixing. Thus, nanoscale ZVI has proved to be a promising remedy for PAH-contaminated soil in this study, as well as an optimistically predictable application for additional pilot and field studies.     

In field arsenic removal from natural water by zero-valent iron assisted by solar radiation

An in situ arsenic removal method applicable to highly contaminated water is presented. The method is based in the use of steel wool, lemon juice and solar radiation. The method was evaluated using water from the Camarones River, Atacama Desert in northern Chile, in which the arsenic concentration ranges between 1000 and 1300 μg L⁻¹. Response surface method analysis was used to optimize the amount of zero-valent iron (steel wool) and the citrate concentration (lemon juice) to be used. The optimal conditions when using solar radiation to remove arsenic from natural water from the Camarones river are: 1.3 g L⁻¹ of steel wool and one drop (ca. 0.04 mL) of lemon juice. Under these conditions, removal percentages are higher than 99.5% and the final arsenic concentration is below 10 μg L⁻¹. This highly effective arsenic removal method is easy to use and inexpensive to implement.     

氧气促进纳米零价铁除砷效果及其作用机制

为了探究氧气对纳米零价铁(nZVI)除砷的影响,考察了不同的氧含量(厌氧、低氧、中氧和高氧)条件下nZVI对As(Ⅲ)/As(V)的去除效果,并结合表征结果分析了氧气对nZVI除砷的影响机制。结果表明：氧气存在会显著促进nZVI对As(Ⅲ)/As(Ⅴ)的去除,但不同氧含量对nZVI除砷的促进程度有所不同;随着氧含量的增加,As(Ⅲ)/As(Ⅴ)的去除率呈现先增大后减小然后再增大的趋势。在初始砷浓度为50 mg·L⁻¹、nZVI投加量为200 mg·L⁻¹、O₂/nZVI摩尔比等于0.5时,砷的去除率达到最大,As(Ⅲ)和As(Ⅴ)体系中砷的去除率分别为96.27%和51.75%。固相表征结果表明：氧气对nZVI的氧化程度及除砷效果具有较大的影响,在低氧条件下,nZVI被少量氧化为无定型铁矿物进而提高除砷效果;在中氧条件下,nZVI被氧化为大量的溶解态Fe(Ⅱ)/Fe(Ⅲ),溶解态铁对砷没有去除效果,从而导致砷的去除率降低;在高氧条件下,nZVI被大量氧化,溶解态Fe(Ⅱ)/Fe(Ⅲ)进一步被氧化形成新的无定型铁矿物,可增强除砷效果。以上结果可为评估不同氧含量条件下纳米零价铁除砷效果以及人为强化纳米零价铁除砷效果提供参考。     

Haloacetic acid removal by sequential zero-valent iron reduction and biologically active carbon degradation

An innovative haloacetic acid (HAA) removal process was developed. The process consisted of a zero-valent iron (Fe⁰) column followed by a biologically active carbon (BAC) column that were efficient in degrading tri- and di-HAAs, and mono- and di-HAAs, respectively. The merit of the process was demonstrated by its performance in removing trichloroacetic acid (TCAA). An empty bed contact time of 10 min achieved nearly complete removal of 1.2 μM TCAA and its subsequent products, dichloroacetic acid (DCAA) and monochloroacetic acid (MCAA). HAA removal was a result of chemical dehalogenation and biodegradation rather than physical adsorption. Preliminary kinetic analyses were conducted and the pseudo-first-order rate constants were estimated at ambient conditions for Fe⁰ reduction of TCAA and biodegradation of DCAA and MCAA by BAC. This innovative process is highly promising in removing HAAs from drinking water, swimming pool water, and domestic or industrial wastewater.     

Simultaneous removal of NO and SO2 by high-temperature fluidized zero-valent iron processes

A new approach to simultaneously remove nitrogen monoxide (NO) and sulfur dioxide (SO2) by zero valent iron (ZVI) was investigated. Three different parameters, temperature, flux, and ZVI dosage, were tested in fluidized ZVI column studies containing 500 ppmv of NO and SO2, respectively. Under the ZVI dosage of 0.5 g at flux of 0.6 L/cm2 x min for temperature 573 K, there is neither NO nor SO2 reduction. For 623 K and 673 K, complete removal for NO and > 90% removal for SO2 were achieved. For temperatures of 723 K and 773 K, 100% removal was achieved for both NO and SO2. The amounts of NO or SO2 reduction (as milligrams of NO or SO2 per gram ZVI) increased as temperature increased, and linearities were observed with both correlation coefficients > 0.97. Compared with NO, SO2 had earlier breakthrough because of a slower diffusion rate and less reactivity but higher mass reduction because of a higher molecular weight for SO2 (64 g/mol for SO2 and 30 g/mol for NO). At same temperature, both NO and SO2 reductions (as milligrams of NO or SO2 per gram of ZVI) were constant regardless of either flux or ZVI dosage variation, but breakthrough time was affected by both flux and ZVI dosage. A parameter weight of ZVI/flux (W/F) was developed to represent these two parameters at the same time to assess the breakthrough time of NO and SO2. Higher breakthrough time was achieved for higher W/F value. Moreover, interestingly, longer breakthrough time and more NO and SO2 mass reduction were achieved for combined NO and SO2 than individual NO or SO2 treated by ZVI, and both oxidation and reduction reactions occurred instead of a reduction reaction only. Chemical reactions among ZVI/NO, ZVI/ SO2, and ZVI/NO/SO2 were also proposed and verified by X-ray diffraction analyses.     

Influence of complex reagents on removal of chromium(VI) by zero-valent iron

The removal of Cr(VI) by zero-valent iron (Fe(0)) and the effect of three complex reagents, ethylenediaminetetraacetic acid (EDTA), NaF and 1,10-phenanthroline, on this reaction were investigated using batch reactors at pH values of 4, 5 and 6. The results indicate that the removal of Cr(VI) by Fe(0) is slow at pH 5.0 and that three complex reagents play different roles in the reaction. EDTA and NaF significantly enhance the reaction rate. The zero-order rate constants at pH 5.0 were 5.44 microM min(-1) in the presence of 4mM EDTA and 0.99 micrM min(-1) in the presence of 8 mM NaF, respectively, whereas that of control was only 0.33 micrM min(-1), even at pH=4.0. This enhancement is attributed to the formation of complex compounds between EDTA/NaF and reaction products, such as Cr(III) and Fe(III), which eliminate the precipitates of Cr(III), Fe(III) hydroxides and Cr(x)Fe(1-)(x)(OH)(3) and thus reduce surface passivation of Fe(0). In contrast, 1,10-phenanthroline, a complex reagent for Fe(II), dramatically decreases Cr(VI) reduction by Fe(0). At pH=4.0, the zero-order rate constant in the presence of 1mM of 1,10-phenanthroline was 0.02 micrM min(-1), decreasing by 99.7% and 93.9%, respectively, compared with the results in the presence and absence of EDTA. The results suggest that a pathway of the reduction of Cr(VI) to Cr(III) by Fe(0) may involve dissolution of Fe(0) to produce Fe(II), followed by reduction of Cr(VI) by Fe(II), rather than the direct reaction between Cr(VI) and Fe(0), in which Fe(0) transfers electrons to Cr(VI).     

Biogas upgrading to methane and removal of volatile organic compounds in a system of zero-valent iron and anaerobic granular sludge

Environmental Science and Pollution Research - The current study presented a novel process of biogas upgrading to biomethane (higher than 97%) based on anaerobic sludge and zero-valent iron (ZVI)...     

基于Fe~0的PRB去除地下水中硝酸盐的模拟研究

由于地下水中硝酸盐污染的普遍性、难去除性和对人体健康的潜在危害性而引起人们的广泛关注。本研究通过柱实验,研究了不同条件(进水pH、砂/Fe0体积比和添加锯末)对基于Fe0的模拟渗透性反应墙(permeable reactivebarrier,PRB)去除地下水中硝酸盐的影响。结果表明,由于黄土的碱性和缓冲作用,进水pH的影响不显著;5~6∶1的砂/Fe0(S/Fe)体积比既可提高铁粉利用率,又有利于硝酸盐的还原并延长PRB的有效期;铁腐蚀产物引起铁粉粘固而导致PRB的渗透性和反应性降低,尤其在反应区的进水口端;虽然酸预处理Fe0有助于硝酸盐的还原,但更容易引起堵塞,而在Fe0体系中加入活性炭不仅可提高硝酸盐的去除率,还可延长PRB的有效期,是一种很好的辅助填料;同时添加锯末和Fe0的生物-化学联合法更有助于硝酸盐还原并提高出水水质,具有很好的应用潜力;不同条件下,出水中的氨和亚硝酸盐的浓度相差较大,但可溶性铁浓度均低于饮用水标准(0.3 mg/L)。Fe0的化学还原和锯末的生物反硝化是硝酸盐去除的主要机理。本研究表明,基于Fe0的PRB用于去除中性或偏碱性地下水中的硝酸盐污染具有很大的潜力。     

天然有机物对零价铁去除水体中砷的影响研究

在研究零价铁对水体中砷去除动力学的基础上,着重探讨了天然有机物腐殖酸对零价铁除砷的影响.并对零价铁的腐蚀产物进行了分析.结果表明,水体中的砷可以通过在零价铁腐蚀产物上的吸附得到快速去除.腐殖酸显著降低了砷的去除率,这归因于腐殖酸与零价铁腐蚀产生的铁离子形成络合物,阻止了Fe(OH)3(或Fe(OH)2)沉淀的产生.腐殖酸浓度越高.砷的去除率越低.1.00 mg腐殖酸最多可以络合约0.75 mg铁离子.当铁离子与腐殖酸的络合达到饱和后,零价铁进一步腐蚀产生的铁离子可形成Fe(OH)3(或Fe(OH)2)沉淀,这些沉淀物可吸附水体中的腐殖酸和砷,从而加速砷的去除.冷冻干燥后的零价铁腐蚀产物的结构以无定型为主,含有少量的结晶化合物,包括γ-Fe2O3、γ-FeO(OH)和Fe3O4等.腐殖酸的存在可进一步增加腐蚀产物中的无定型成分.光电能谱(XPS)分析结果显示,吸附在腐蚀产物上的砷为5价,没有发现5价砷被还原成3价砷.在应用零价铁修复砷污染水体时,应考虑腐殖酸的影响.     

零价铁与甲醇支持的生物-化学法去除富氧水中的硝酸盐氮

针对富氧水中硝酸盐氮（NO3--N）,采用零价铁（ZVI）和甲醇支持的生物-化学联合法开展了批实验研究,探讨了ZVI类型、CH3OH：N比、初始溶解氧（DO）浓度、初始NO3--N浓度和水温等5个因素对联合法除氧脱氮效果的影响。结果表明,ZVI的除氧能力由高至低依次为：ZVI-C（0.124 d）>ZVI-A（0.141 d）>ZVI-B（0.179 d）。ZVI支持的联合法NO3--N去除率由高至低依次为：ZVI-A（99.6%）>ZVI-C（95.3%）>ZVI-B（92.2%）。CH3OH：N≤3.5：1时,联合法去除3--N;CH3OH：N=10：1时,去除100%的NO3--N;CH3OH：N=200：1时,去除70.2%的NO3--N。当初始DO浓度介于3.6~5.3 mg/L之间时,联合法的NO3--N去除率介于98.8%~99.6%之间。在任意时刻,低底物浓度（5.2 mg/L）时的NO3--N去除率低于高浓度（21.1 mg/L）时的去除率;低底物浓度下完全脱氮所需时间比高浓度下长2 d。15.0℃时联合法需要7 d可以达到完全脱氮,然而在27.5℃时则需要5 d。低温时亚硝酸盐氮浓度最大值（4.4 mg/L）显著高于高温时的最大值（1.1 mg/L）。ZVI类型、CH3OH：N、初始NO3--N浓度和水温显著影响联合法的脱氮效果,而初始DO浓度对联合法的影响不大。     

超声强化Fe0去除阳离子红GTL的研究

采用US/Fe0系统去除阳离子红GTL,考察了pH值、Fe0用量、超声功率及活性炭、H2O2、盐分添加对阳离子红GTL去除率的影响,利用紫外-可见吸收光谱变化查明阳离子红GTL在不同条件下的去除差异性,利用SEM解析铁的形态与染料去除的相关性。结果表明： pH≥5.0时超声和Fe0具有协同效应,Fe0用量2 g/L,pH=7.0,超声功率135 W,阳离子红GTL去除率达到96.07%;一定量的活性炭、H2O2、盐分添加会加速染料去除,US加速Fe0反应速度,但不改变染料降解机理,添加活性炭能够彻底降解阳离子红GTL,添加H2O2提供的氧化环境抑制苯胺类化合物生成;铁的形态及与染料的接触是影响染料去除效果的重要原因。     

Effective adsorbent for arsenic removal: core/shell structural nano zero-valent iron/manganese oxide

Recently, nano zero-valent iron (nZVI) has emerged as an effective adsorbent for the removal of arsenic from aqueous solutions. However, its use in various applications has suffered from reactivity loss resulting in a decreased efficiency. Thus, the aim of this study was to develop an effective arsenic adsorbent as a core/shell structural nZVI/manganese oxide (or nZVI/Mn oxide) to minimize the reactivity loss of the nZVI. As the major result, the arsenic adsorption capacities of the nZVI/Mn oxide for As(V) and As(III) were approximately two and three times higher than that of the nZVI, respectively. In addition, the As(V) removal efficiency of the nZVI/Mn oxide was maintained through 4 cycles of regeneration whereas that of the nZVI was decreased significantly. The enhanced reactivity and reusability of the nZVI/Mn oxide can be successfully explained by the synergistic interaction of the nZVI core and manganese oxide shell, in which the manganese oxides participate in oxidation reactions with corroded Fe²⁺ and subsequently retard the release of aqueous iron providing additional surface sites for arsenic adsorption. In summary, this study reports the successful fabrication of a core/shell nZVI/Mn oxide as an effective adsorbent for the removal of arsenic from aqueous solutions.     

超声波/零价铁降解对硝基苯胺的试验研究

对在超声波、零价铁和超声波/零价铁(U/Fe0)等体系中对硝基苯胺的降解规律进行了研究。研究结果表明,对硝基苯胺在超声波作用下,降解规律符合一级反应动力学模型,但超声波对高浓度的对硝基苯胺降解效果较差。在U/Fe0体系中,超声波和零价铁对降解对硝基苯胺具有协同作用,对硝基苯胺降解速率显著提高。降解机理显示,对硝基苯胺在零价铁表面上发生原电池反应,被还原为对苯二胺,在超声波作用下进一步降解。在U/Fe0体系中添加Cu2+,形成Fe/Cu原电池,可进一步促进对硝基苯胺的降解速率,降解效率优于铸铁屑形成的Fe/C原电池。     

Effect of amorphous silica and silica sand on removal of chromium(VI) by zero-valent iron

The effect of two surfaces (amorphous silica and silica sand) on the reduction of chromium(VI) by zero-valent iron (Fe(0)) was investigated using batch reactors. The amendment of both surfaces significantly increased the rate and extent of Cr(VI) removal. The rate enhancement by amended surfaces is presumed to result from scavenging of Fe(0)-Cr(VI) reaction products by the provided surfaces, which minimized surface deactivation of Fe(0). The rate enhancing effect was greater for silica compared to sand, and the difference is attributed to silica's higher surface area, greater affinity for reaction products and pH buffering effect. For a given mass of Fe(0), the reactivity and longevity of Fe(0) to treat Cr(VI) increased with increasing dose of silica. Elemental analyses of the reacted iron and silica revealed that chromium removed from the solution was associated with both surfaces, with its mass distribution being approximately 1:1 per mass of iron and silica. The overall result suggests reductive precipitation was a predominant Cr(VI) removal pathway, which involves initial reduction of Cr(VI) to Cr(III), followed by formation of Cr(III)/Fe(III) hydroxides precipitates.     

纳米零价铁处理冶炼废水

多年的理论和机制研究发现,纳米零价铁（NZVI）作为还原剂及吸附剂,可处理水溶液中的多种重金属及类金属物质;而高效处理含高浓度重金属且成分复杂的冶炼废水是一项技术难题。本研究针对特定的冶炼废水（高浓度重金属及砷、高浓度氨氮、低pH、高含盐量）,研究了pH及NZVI投加量对砷、铜、锌、铅、镍的处理效果,并考察了连续流反应器中水力停留时间（HRT）及NZVI投加量对处理效果的影响。实验通过电感耦合等离子体发射光谱仪（ICP-OES）进行水样测试,扫描电子显微镜（SEM）、X射线衍射仪（XRD）进行固相表征。实验表明,通过NZVI处理,砷、铜、锌、铅、镍去除率均达99%以上,出水浓度均小于0.1 mg/L,达到废水排放标准（GB 8978-1996）。通过连续流反应器的应用发现,适当增大HRT、增加NZVI投加量,有利于更长时间保证出水水质的良好,延长NZVI消耗时间,提高废水处理量。结果显示,NZVI对复杂冶炼废水有极好的处理效果,在废水处理领域有着独特的优势,为后续研究及实际应用提供借鉴。