零价铁与厌氧微生物协同还原地下水中的硝基苯

通过间歇式实验,考察了零价铁与厌氧微生物协同还原地下水中硝基苯的效果。实验结果表明,由零价铁腐蚀为厌氧微生物提供H2电子供体还原硝基苯的效果明显优于零价铁和微生物单独作用,硝基苯去除率分别提高21.8%和57.0%。弱酸性条件有利于协同反应进行,当初始pH为5.0和6.0时,4 d后硝基苯去除率比初始pH为7.0时的提高74.4%和35.2%。增加零价铁投加量可提高协同还原的效果,零价铁最佳投加量为250 mg/L。零价铁腐蚀产生的Fe2+无法作为电子供体被微生物利用,但可作为无机营养元素促进协同过程。由于零价铁产H2速率受表面覆盖物影响不明显,在地下水修复过程中可保证协同效果并延长零价铁的使用寿命。     

纳米零价铁和零价铁对餐厨垃圾暗发酵制氢过程铁离子和酶活性的影响

通过投加不同浓度的纳米零价铁(NZVI)和零价铁(ZVI),考察了暗发酵制氢过程中铁离子组成和浓度变化、氢化酶和脱氢酶活性,研究了2种添加剂强化餐厨垃圾高温((55±1) ℃)暗发酵制氢的作用机制。结果表明：投加NZVI和ZVI均可提高餐厨垃圾暗发酵制氢性能;当投加100 mg·L⁻¹ ZVI时,产氢效果最佳,最大产氢潜力和最大产氢速率分别为425.72 mL和66.32 mL·h⁻¹,是投加NZVI实验组的1.64倍和1.34倍,代谢途径是以乙醇型发酵为主的混合型发酵;在投加NZVI和ZVI后,暗发酵制氢末端产物的Fe²⁺和Fe³⁺浓度升高,投加300 mg·L⁻¹ NZVI和100 mg·L⁻¹ ZVI实验组Fe²⁺浓度最大,是未投加实验组的2倍和1.87倍;与反应前相比,Fe²⁺显著升高,Fe³⁺由于微生物利用与转化浓度降低,同时可有效提高氢化酶活性。投加100 mg·L⁻¹ ZVI不仅可提高氢化酶活性,还可提高脱氢酶活性。以上结果可为提高餐厨垃圾等复杂有机废物的高效能源化提供参考。     

A comparison of the low frequency electrical signatures of iron oxide versus calcite precipitation in granular zero valent iron columns

Geophysical methods have been proposed as technologies for non-invasively monitoring geochemical alteration in permeable reactive barriers (PRBs). We conducted column experiments to investigate the effect of mineralogy on the electrical signatures resulting from iron corrosion and mineral precipitation in Fe0 columns using (a) Na2SO4, and (b) NaHCO3 plus CaCl2 mixture, solutions. At the influent interface where the reactions were most severe, a contrasting time-lapse electrical response was observed between the two columns. Solid phase analysis confirmed the formation of corrosion halos and increased mineralogical complexity in the corroded sections of the columns compared to the minimal/non-corroded sections. We attribute the contrasting time-lapse signatures to the differences in the electrical properties of the mineral phases formed within the two columns. While newly precipitated/transformed polarizable and semi-conductive iron oxides (mostly magnetite and green rust) increase the polarization and conductivity of the sulfate column, the decrease of both parameters in the bicarbonate column is attributed to the precipitation of non-polarizable and non-conductive calcite. Our results show that precipitate mineralogy is an important factor influencing the electrical properties of the corroded iron cores and must be considered if electrical geophysical methods are to be developed to monitor PRB barrier corrosion processes in situ.     

Zero valent iron mediated degradation of the pharmaceutical diazepam

Parameters that influence the zero valent iron mediated degradation of the pharmaceutical diazepam (DZP) were evaluated including the iron concentration and its pre-treatment, the effect of complexation with EDTA and oxic versus anoxic condition. It was observed that acid pre-treatment of iron particles is important for degradation efficiency and that H₂SO₄ is a better choice than HCl, resulting in higher degradation of DZP. Under oxic conditions, the degradation of DZP achieved 96% after 60 min using Fe⁰ (25 g L⁻¹) pre-treated with H₂SO₄ in the presence of EDTA (119 mg L⁻¹), while mineralization achieved around 60% after the same time. Under anoxic conditions, degradation occurred, however at lower extent, achieving 67% after 120 min. The addition of EDTA improved the treatment efficiency in 20% leading to 99% DZP degradation after 120 min. The first intermediates formed during DZP degradation were identified using LC/MS analysis and revealed the formation of mono- and di-hydroxylated products from DZP during Fe⁰/EDTA/O₂ degradation, which evidences that OH was the main oxidizing species formed in this process.     

零价铁复合有机膨润土处理染料废水的研究

针对目前印染废水处理现状及膨润土在水处理中回收困难等问题,提出将零价铁复合到有机膨润土中制成零价铁复合有机膨润土(ZVI-OB),以达到高效吸附并降解污染物的目的。以染料废水(Orange II) 作为研究对象,考察了废水中染料的初始浓度、pH以及吸附时间对ZVI-OB去除染料效率的影响,并研究了吸附后降解过程中时间和pH对污染物降解的影响以及降解前后膨润土层结构的变化。研究结果表明,ZVI-OB相对于CTMAB改性的有机膨润土而言,其吸附量有所降低,但ZVI-OB在吸附污染物之后能有效降解有机物。ZVI-OB在饱和吸附Orange II后经催化氧化,总有机碳含量降低为原来的19%,可以重复利用。     

超声波和零价铁联用对氯代苯酚脱氯降解作用的研究

采用超声波和零价铁联用对氯代有机物3氯苯酚(CP)、2,4-二氯苯酚(DCP)和2,4,6-三氯苯酚(TCP)模拟废水进行了脱氯处理研究。以单因素法, 考察了铁粉初始投加量、溶液的初始浓度、超声波功率和溶液的pH值等因素对氯代酚降解的影响,并探讨了降解反应动力学。结果表明,超声波和零价铁联用对氯酚具有显著的降解效果,当水样初始浓度为25 mg/L,溶液pH呈弱酸性,超声波功率为200 W时,氯代酚的脱氯效率达到最大值。降解反应符合准一级反应,CP、DCP和TCP的反应速率常数分别0.0613 h^-1、0.374 h^-1和0.197 h^-1。     

改性凹凸棒土负载纳米铁的制备及性能

以200目的天然凹凸棒土为原料,先对原土进行酸活化与微波改性,再以改性凹凸棒土为载体,采用液相还原法由FeCl3·6H2O和NaBH4制备改性凹凸棒土负载纳米铁。通过正交实验、扫描电镜（SEM）、能谱仪（EDS）及红外光谱（IR）对负载前后的凹凸棒土进行表征分析确定其最佳条件。并通过稳定性实验和去除实验对改性凹凸棒土负载纳米铁的性能分析。结果表明：改性凹凸棒土负载纳米铁的最佳条件是铁土比为2.5：1,酸浓度为3 mol·L-1,微波时间为6 min,微波功率为600 W,改性时间为24 h。改性凹凸棒土负载纳米铁在常规水处理环境中能稳定存在。对水中的Cr（Ⅵ）有良好的去除效果,去除率可达97.67%。     

零价铁修复受三氯乙烯污染地下水的实验研究

通过批实验和柱实验研究了三氯乙烯（TCE）初始浓度、四氯乙烯(PCE)等对零价铁去除三氯乙烯的影响,并建立了三氯乙烯降解的反应动力学方程。结果表明：（1）零价铁对TCE具有较好的降解效果,反应符合准一级反应动力学方程,表观反应速率常数随TCE浓度的增加而减小;（2）在铁粉充足的条件下,TCE初始浓度对降解效果影响不显著,且TCE去除率皆可达到90%以上;（3）PCE的存在抑制了TCE的脱氯反应。PCE和TCE共存时,TCE的最大去除率仅为64.2%;TCE脱氯反应的表观反应速率明显降低,反应半衰期由TCE单独存在时的6.8～9.7 h增大到66 h～346.5 h。     

零价铁活化过硫酸钠体系降解污染土壤中的多环芳烃

采用Fe0活化Na2S2O8体系降解污染土壤中的PAHs,其代表化学物为NAP、PHE、FLA和BAP。分别研究了Na2S2O8的添加量、Na2S2O8与Fe0的物质的量比、水土比和温度对降解效果的影响,同时探讨了PAHs的降解动力学;并利用电子顺磁共振法(EPR)验证了Fe0活化Na2S2O8的自由基产生情况。结果表明,当1 mol·L-1的Na2S2O8添加量为10 mL、Na2S2O8与Fe0物质量之比为200∶1、水土比为2∶1、温度为60 ℃时反应36 h后,NAP、PHE、FLA、BAP的降解率分别为98.15%、78.41%、93.47%和97.64%。PAHs的降解符合一级反应动力学,且BAP的反应速率常数最大为0.030 5 h-1。EPR谱图表明,Fe0活化Na2S2O8降解PAHs污染的土壤是SO4-·和·OH共存的反应体系。该研究可为Fe0活化Na2S2O8体系降解PAHs污染土壤的机理提供一定的依据。     

零价铁耦合芬顿氧化法处理TNT红水

采用零价铁耦合芬顿氧化法处理TNT红水,研究了初始pH、零价铁投加量、过氧化氢（H2O2）投加量及温度对红水中总有机碳（TOC）去除效果的影响,同时进行了TOC去除过程中反应动力学的探讨。结果表明,零价铁耦合芬顿氧化体系可有效降解TNT红水中的2,4-二硝基甲苯-3-磺酸钠和2,4-二硝基甲苯-5-磺酸钠。在初始pH为2,温度为20 ℃的条件下,加入1.5 g·L-1零价铁反应1 h后,再加入100 mL·L-1H2O2反应4 h,红水中二硝基甲苯磺酸盐浓度从500 mg·L-1降至0 mg·L-1,去除率为100%,TOC浓度从150 mg·L-1降至30 mg·L-1,去除率达到80%。反应中TOC的降解过程遵循拟二级反应动力学方程。零价铁耦合芬顿氧化法可以作为TNT红水的有效处理途径。     

Enhanced removal of pentachlorophenol by a novel composite: nanoscale zero valent iron immobilized on organobentonite

Nanoscale zero valent iron (NZVI) was immobilized on the organobentonite (CTMA-bent), so as to enhance the reactivity of NZVI and prevent its aggregation. This novel composite (NZVI/CTMA-Bent) was characterized by transmission electron microscope and X-ray diffraction. Good dispersion of NZVI particles on the bentonite was observed. Its performance on removing pentachlorophenol (PCP) was investigated by batch experiments. Results showed NZVI/CTMA-Bent could rapidly and completely dechlorinate PCP to phenol with an efficiency of 96.2%. It was higher than the sum (54.5%) of reduction by NZVI (31.5%) and adsorption by CTMA-Bent (23.0%) separately. The kinetic studies indicated the removal rate of PCP was positively related to the adsorption. We proposed that the adsorption of PCP by CTMA-Bent enhanced the mass transfer of PCP from aqueous to iron surface. Besides, NZVI/CTMA-Bent exhibited good stability and reusability, and CTMA-Bent could also reduce the amount of iron ions released into the solution.     

Impact of pH buffer capacity of sediment on dechlorination of atrazine using zero valent iron

This research investigated the role of the pH buffer capacity of sediment on the dechlorination of atrazine using zero valent iron (ZVI). The buffer capacity of the sediment was quantified by batch experiments and estimated to be 5.0 cmol OH^? · pH^?1. The sediments were spiked with atrazine at 7.25-36.23 mg kg^?1 (6.21 × 10^?7–3.09 × 10^?6 mol atrazine · g^?1 sediment) for the batch experiments. The buffer capacity of the sediment maintained the sediment suspension at neutral pH, thereby enabling continuous dechlorination until the buffer capacity of the sediment was depleted. The pseudo-first order dechlorination constants were estimated to be in the range of 1.19 × 10^?2?7.04 × 10^?2 d^?1 for the atrazine-spiked sediments.     

零价铁强化城市污泥与垃圾焚烧厂渗滤液协同厌氧消化

针对城市污泥(初沉污泥、剩余污泥)和垃圾焚烧厂渗滤液2种市政废物的协同厌氧消化产气量不足的问题,采用投加零价铁的方式,探究零价铁对厌氧消化过程中产酸和产甲烷阶段的强化作用,并研究消化前后COD、VSS、氨氮以及上清液离子的变化。以初沉污泥与剩余污泥体积比4∶1、渗滤液添加量为15%的基质作为底物,投加不同浓度零价铁进行厌氧消化。结果表明：零价铁能有效提升协同厌氧消化系统中总挥发性脂肪酸产量、促进丙酸分解、进一步降解复杂有机物;当零价铁投入量为4 g·L⁻¹时,累计产甲烷量最高达189.65 mL·g⁻¹(以VSS计),相比对照组提升了30.1%,其产气速率符合一次函数和Scholl Canyon模型指数衰减规律;在25 g·L⁻¹和40 g·L⁻¹的高投加量零价铁条件下,产气高峰提前,但累计甲烷产量低于对照组;随着零价铁的投加量增加,COD降解率呈下降趋势,VSS降解率提升,氨氮变化不大;此外,消化液上清液中,正磷酸盐、硫酸根浓度明显减少,这与亚铁离子的混凝沉淀作用相关,同时也是削弱零价铁强化作用的原因之一。研究结果可为城市污泥和垃圾焚烧厂渗滤液协同厌氧消化提供参考。     

Modelling of sequential groundwater treatment with zero valent iron and granular activated carbon

Multiple contaminant mixtures in groundwater may not efficiently be treated by a single technology if contaminants possess rather different properties with respect to sorptivity, solubility, and degradation potential. An obvious choice is to use sequenced units of the generally accepted treatment materials zero valent iron (ZVI) and granular activated carbon (GAC). However, as the results of this modelling study suggest, the required dimensions of both reactor units may strongly differ from those expected on the grounds of a contaminant-specific design. This is revealed by performing an analysis for a broad spectrum of design alternatives through numerical experiments for selected patterns of contaminant mixtures consisting of monochlorobenzene, tetrachloroethylene, trichloroethylene (TCE), cis-1,2-dichloroethylene (cis-DCE), and vinyl chloride (VC). It is shown that efficient treatment can be achieved only if competitive sorption effects in the GAC unit as well as the formation of intermediate products in the ZVI unit are carefully taken into account. Cost-optimal designs turned out to vary extremely depending on the prevailing conditions concerning contaminant concentrations, branching ratios, and unit costs of both reactor materials. Where VC is the critical contaminant, due to high initial concentration or extensive production as an intermediate, two options are cost-effective: an oversized ZVI unit with an oversized GAC unit or a pure GAC reactor.     

Discussion of Chicgoua Noubactep on “Removal of thiobencarb in aqueous solution by zero valent iron” by Md. Nurul Amin et al. [Chemosphere 70 (3) (2008) 511–515]

The following comments are proposed to clarify some related issues on the use of zero valent iron micrometric particles for the treatment of a thiobencarb pesticide solution published in a recent article by Nurul Amin et al., [Nurul Amin Md., Kaneco, S., Kato, T., Katsumata, H., Susuki, T., Otha, K., 2008. Removal of thiobencarb in aqueous solution by zero valent iron. Chemosphere 70 (3), 511–515], and discussed later by Chicgoua Noubactep.     

Zero valent iron remediation of a mixed brominated ethene contaminated groundwater

The suitability of a granulated zero valent iron (ZVI) permeable reactive barrier (PRB) remediation strategy was investigated for tribromoethene (TriBE), cis-1,2-dibromoethene (c-DBE), trans-1,2-dibromoethene (t-DBE) and vinyl bromide (VB), via batch and large-scale column experiments that were subsequently analysed by reactive transport modelling.The brominated ethenes in both batch and large-scale column experiments showed rapid (compared to controls and natural attenuation) degradation in the presence of ZVI. In the large-scale column experiment, degradation half-lives were 0.35 days for TriBE, 0.50 days for c-DBE, 0.31 days for t-DBE and 0.40 days for VB, under site groundwater flow conditions, resulting in removal of brominated ethenes within the first 0.2 m of a 1.0 m thick ZVI layer, indicating that a PRB groundwater remediation strategy using ZVI could be used successfully.In the model simulations of the ZVI induced brominated ethene degradation, assuming a dominant reductive β-elimination pathway via bromoacetylene and acetylene production, simulated organic compound concentrations corresponded well with both batch and large-scale column experimental data. Changes of inorganic reactants were also well captured by the simulations. The similar ZVI induced degradation pathway of TriBE and TCE suggests that outcomes from research on ZVI induced TCE remediation could also be applied to TriBE remediation.     

Pressurized CO2/zero valent iron system for nitrate removal

A fluidized zero valent iron (ZVI) reactor pressurized by CO(2) gas for controlling pH was employed for nitrate reduction. The proposed CO(2) pressurized system potentially has advantages of using less CO(2) gas and reaching equilibrium pH faster than CO(2)-bubbled system. However, due to weak acid nature of carbonic acid, system pH gradually increased with increasing oxidation of ZVI and reduction of nitrate. As pH increased with progress of reaction, nitrate removal rate decreased continuously. The results indicate that nitrate removal efficiency increases with increasing initial ZVI dosage but reaches plateau at ZVI doses of higher than 8.25gl(-1), and initial nitrate concentration up to 100mg l(-1) as N has minimal impact on the removal efficiency. Unlike the fluidized system with pH control by strong acid reported in our pervious study, near 100% of nitrogen recovery was observed in the current process, indicating that nitrate reduction by ZVI with different pH controlled mechanisms will have different reaction routes.     

球磨硫化零价铁活化过硫酸盐降解水体中有机氯农药

利用球磨技术制备了不同硫铁(S/Fe)摩尔比的硫化零价铁(S-mZVI),并与过硫酸钠(PS)组成复合氧化体系(S-mZVI/PS),用于降解水体中的4,4′-DCBP和β-HCH,探索了制备参数和环境因子对有机氯农药降解效果的影响。结果表明：球磨过程中硫的加入不仅可以实现零价铁的硫化,还能提高零价铁的球磨效率。与球磨零价铁相比,S-mZVI的颗粒分散更均匀,呈不规则球状,且S/Fe摩尔比越大颗粒表面越平滑,更接近于球形。S-mZVI/PS体系较mZVI/PS体系对4,4′-DCBP和β-HCH的催化降解活性更高,且随着S/Fe摩尔比的增大,mZVI的腐蚀速率越高,其对污染物的降解效果越好。当S/Fe摩尔比为0.10、PS/Fe投加量配比为1/2时,4,4′-DCBP和β-HCH的降解效果最好,反应120 min后两者的最终降解率分别为92.4%和93.0%。而且,随着pH的升高,4,4′-DCBP和β-HCH降解效率逐渐降低,但二者最终降解率之间的差异较小。腐殖酸和$ {{\rm{HC}}{{\rm{O}}^ -_3} }$的存在会降低4, 4′-DCBP和β-HCH的降解效率,且随着腐殖酸和${ {\rm{HC}}{{\rm{O}}^ -_3}} $浓度的增加,对其降解效果的抑制作用增强;而$ {{\rm{N}}{{\rm{O}}^ -_3}} $的存在及浓度变化对S-mZVI/PS体系中4,4′-DCBP和β-HCH的降解影响较小。因此,S-mZVI可显著提高PS的活化效率及其对有机氯农药的降解速率,适合用作有机氯农药污染水体的修复。     

Zerovalent iron encapsulated chitosan nanospheres - a novel adsorbent for the removal of total inorganic arsenic from aqueous systems

Evaluation of Chitosan zerovalent Iron Nanoparticle (CIN) towards arsenic removal is presented. Addition of chitosan enhances the stability of Fe(0) nano particle. Prepared adsorbent was characterized by FT-IR, SEM EDX, BET and XRD. It was found that, with an initial dose rate of 0.5 g L⁻¹, concentrations of As (III) and As (V) were reduced from 2 mg L⁻¹ to <5 μg L⁻¹ in less than 180 min and the adsorbent was found to be applicable in wide range of pH. Langmuir monolayer adsorption capacity was found to be 94 ± 1.5 mg g⁻¹ and 119 ± 2.6 mg g⁻¹ at pH 7 for As (III) and As (V) respectively. Major anions including sulfate, phosphate and silicate did not cause significant interference in the adsorption behavior of both arsenite and arsenate. The adsorbent was successfully recycled five times and applied to the removal of total inorganic arsenic from real life groundwater samples.     

Relevance study of bare and coated zero valent iron nanoparticles for lindane degradation from its by-product monitorization

Zero-valent iron nanoparticles (NZVI) as well as polymer–stabilized nanoparticles were synthesized and used for lindane (γ-hexachlorocyclohexane) degradation in aqueous solution. To study the effectiveness of the different coated nanoparticles, simple and rapid analytical methods have been developed to measure and to detect lindane and its by-products. For the monitorization of lindane degradation solid-phase extraction (SPE) was used, while volatile by-products formation measurement was carried out by headspace-solid phase microextraction (HS–SPME) followed by GC/MS. The SPE–GC/MS method provides low detection limits (0.2 μg L⁻¹), high recovery (above 95%) and it is a valuable tool for kinetic studies of the degradation process for each polymer used, while HS–SPME–GC/MS has proved to be an effective tool for the extraction and evaluation of volatile degradation by-products.