硝酸根对零价铁去除地下水中六价铬的影响

通过批实验和连续通流的柱模拟实验对比研究了存在NO3-和不存在NO3-条件下零价铁（Fe0）去除Cr（Ⅵ）的反应特征,并对比分析了NO3-对零价铁（Fe0）去除Cr（Ⅵ）的影响。批实验结果表明,在不同初始pH条件下,NO3-的加入均使得零价铁（Fe0）去除Cr（Ⅵ）的速率升高;当初始pH=7时,NO3-的促进作用最强,反应速率是无NO3-条件下的2.1倍。柱实验结果表明,NO3-的加入使得Fe0去除Cr（Ⅵ）的反应分成了3个不同的阶段：高效期（1025 PV）。在高效期,反应中的NO3-表现为对Fe0反应位点的竞争,抑制了Cr（Ⅵ）还原。在后期的2个阶段中,反应中NO3-则呈现明显的促进作用。NO3-的存在使得零价铁（Fe0）柱趋于整体性同步钝化,延长了Fe0柱的运行寿命,并且增加了零价铁（Fe0）柱对Cr（Ⅵ）的去除效率。NO3-对Fe0去除Cr（Ⅵ）反应的促进作用原因是由于NO3-与Fe0反应产生Fe3O4,Fe3O4可以还原Cr（Ⅵ）,并且具有阻滞反应的产物在Fe0表面堆积和促进电子传导作用。     

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。     

石墨烯/二氧化硅负载纳米零价铁对As(Ⅲ)的去除

以氧化石墨烯和正硅酸乙酯为原料,采用溶胶-凝胶法制得石墨烯/二氧化硅复合材料(GS),以GS为基体,采用液相还原法,得到石墨烯/二氧化硅负载纳米零价铁(NZVI/GS),将其用于水中As(Ⅲ)的吸附研究。通过XRD、TEM、BET、Zeta电位等表征手段对NZVI/GS进行表征。探讨不同反应条件对NZVI/GS的吸附影响,并进行动力学方程和吸附等温线方程拟合。结果表明,NZVI/GS对As(Ⅲ)具有良好的去除效果,当初始溶液pH为6~8,投加量为0.4 g·L-1,反应温度为35 ℃,砷初始浓度为2 mg·L-1时,NZVI/GS对As(Ⅲ)的去除率高达99.81%。通过Langmuir等温吸附方程得到NZVI/GS对As(Ⅲ)最大吸附量55.93 mg·g-1。     

零价纳米铁去除ReO4-的研究

采用NaBH4与FeSO4液相还原法制备零价纳米铁,用制得的零价纳米铁去除ReO4-,然后用分光光度法在610 nm处测定ReO4-的吸光度,从而计算零价纳米铁对ReO4-的去除率.结果表明:(1)ReO4-初始浓度越低,反应速率越快,对最终ReO4-去除率影响不大.(2)pH对反应产生很大影响,将溶液pH调至中性或微...     

微生物燃料电池-零价铁耦合工艺的构建及除砷性能

为了更为有效地利用微生物燃料电池(MFC)所产电能并提高零价铁(ZVI)去除污染物工艺的效率,构建了微生物燃料电池-零价铁(MFC-ZVI)耦合工艺,并将其应用在三价砷水溶液的处理中。实验结果表明,在该耦合系统中,ZVI直接利用了MFC所产生的低压电能,铁腐蚀速率和除砷效率因此得到显著提高。实验所用MFC的最高稳定产电电压为0.52 V,电解过程中MFC的库伦效率为4.59%,以二价铁离子计算的电流效率为72.74%。反应结束后,溶液的pH值由反应前的8.0升高到8.5。两体系中铁氧化物产生量的差异以及铁氧化物形态分布的不同可能是导致其除砷效果不同的主要原因。     

膨润土负载硫化纳米零价铁去除对硝基苯酚的研究

以具有较大比表面积和良好吸附性能的膨润土作为载体,制备了膨润土负载硫化纳米零价铁,并利用X射线光电子能谱(XPS)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)以及比表面积等手段表征膨润土负载硫化纳米零价铁的特性。研究了膨润土负载硫化纳米零价铁的硫铁比(摩尔比)、投加量、初始pH对对硝基苯酚(PNP)去除的影响,并对PNP降解机理进行了初步探究。结果表明,膨润土负载硫化纳米零价铁比表面积为33.06m~2/g,大于膨润土的比表面积(26.72m~2/g),负载的纳米零价铁颗粒分散均匀。当硫铁比为0.011 2、投加量为0.5g/L、初始pH为5.0时,10min基本能把1L1.5mmol/L的PNP完全降解,具有最大的去除速率和去除率。PNP的最主要降解产物为对氨基苯酚。     

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。     

纳米零价铁与黑曲霉发酵液联用对砷锑污染土壤的淋洗修复

土壤砷 (As) 、锑 (Sb) 污染对生态环境和人体健康有着潜在的风险,采用黑曲霉发酵液 (FB) 与纳米零价铁 (nZVI) 联用淋洗修复As、Sb污染土壤。通过振荡淋洗实验,探究nZVI强化FB淋洗去除As、Sb的效果及不同条件下对As、Sb淋洗效率的影响。结果表明,制备的FB对污染土壤中As和Sb有着较好的去除效果,去除率可达84.1%和71.8%;nZVI对FB去除As、Sb有强化作用,在nZVI质量浓度为0.1 g·L⁻¹、pH为1和淋洗时间为60 min的条件下,其淋洗效果最佳,对As、Sb淋洗效率可达96.6%和95.6%,修复后的土壤达到《土壤环境质量 建设用地土壤污染风险管控标准 (试行) 》 (GB 36600-2018) 二类用地标准。nZVI-FB对土壤中As、Sb的解吸动力学符合拟二级动力学方程。nZVI-FB能够有效的提取土壤中As、Sb的铁铝氧化物结合态。本研究结果可为As、Sb复合污染土壤的淋洗修复提供参考。     

小分子有机酸对纳米铁稳定砷的影响

金矿开采后的尾矿中含有大量的砷,纳米零价铁可以有效稳定尾矿中的砷,但是在尾矿的后期复垦过程中,表层植被分泌的小分子有机酸,会使土壤中稳定的砷重新释放,造成二次污染。以植物根系分泌的常见小分子有机酸中的乙酸作为研究对象,在纳米零价铁（NZVI）去除砷的动力学基础上,利用批实验方法研究乙酸对稳定砷的影响过程。结果表明,纳米铁可以在几分钟内去除尾矿浸出液中的砷,反应符合准二级动力学模型,铁砷质量比约500∶1时,砷去除率可以达到94%以上。NZVI快速去除As（Ⅴ）主要是在NZVI表面的氧化铁上发生吸附、共沉淀作用。有氧条件下的NZVI对As（Ⅴ）去除效果优于无氧条件下的效果,长期有氧腐蚀NZVI对浮选尾矿和生物氧化尾矿的砷去除率比未腐蚀的分别增加了18.03%和15.21%。乙酸盐对长期有氧腐蚀NZVI稳定的浮选尾矿和生物氧化尾矿砷的解吸率比未腐蚀的分别减少了7.56%和20.01%。当乙酸（以三水合乙酸钠计）与纳米铁的质量比达到2.72∶1时,由于乙酸的羧基与砷酸根有相似的电荷类型,可以与砷竞争吸附铁氧化物表面的吸附位点,又可以与三价铁离子形成稳定的配合物,会使稳定的砷重新释放。但当铁砷质量比逐渐增大（大于5 000∶1）,较多的吸附位点会有效抑制乙酸盐对砷的释放。     

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.     

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.     

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.     

Influence of organic matter on arsenic removal by continuous flow electrocoagulation treatment of weakly mineralized waters

The aim of this study is to evaluate and understand the electrocoagulation/flocculation (ECF) process to remove arsenic from both model and natural waters with low mineral content and to compare its performances to the coagulation/flocculation (CF) process already optimized. Experiments were thus conducted with iron electrodes in the same specific treatment conditions (4≤current density (mAcm(-2))≤33) to study the influence of organic matter on arsenic removal in conditions avoiding the oxidation step usually required to improve As(III) removal. The process performance was evaluated by combining quantification of arsenic residual concentrations and speciation and dissolved organic carbon residual concentrations with zeta potential and turbidity measurements. When compared to CF, ECF presented several disadvantages: (i) lower As(V) removal yield because of the ferrous iron dissolved from the anode and the subsequent negative zeta potential of the colloidal suspension, (ii) higher residual DOC concentrations because of the fractionation of high molecular weight compounds during the treatment leading to compounds less prone to coagulate and (iii) higher residual turbidities because of the charge neutralization mechanisms involved. However, during this process, As(III) was oxidized to As(V) improving considerably its removal whatever the matrix conditions. ECF thus allowed to improve As(III) removal without applying an oxidation step that could potentially lead to the formation of toxic oxidation by-products.     

Adsorption of natural organic matter from waters by iron coated pumice

Natural pumice particles were used as granular support media and coated with iron oxides to investigate their adsorptive natural organic matter (NOM) removal from waters. The impacts of natural pumice source, particle size fraction, pumice dose, pumice surface chemistry and specific surface area, and NOM source on the ultimate extent and rate of NOM removal were studied. All adsorption isotherm experiments were conducted employing the variable-dose completely mixed batch reactor bottle-point method. Iron oxide coating overwhelmed the surface electrical properties of the underlying pumice particles. Surface areas as high as 20.6m(2)g(-1) were achieved after iron coating of pumice samples, which are above than those of iron coated sand samples reported in the literature. For all particle size fractions, iron coating of natural pumices significantly increased their NOM uptakes both on an adsorbent mass- and surface area-basis. The smallest size fractions (<63 microm) of coated pumices generally exhibited the highest NOM uptakes. A strong linear correlation between the iron contents of coated pumices and their Freundlich affinity parameters (K(F)) indicated that the enhanced NOM uptake is due to iron oxides bound on pumice surfaces. Iron oxide coated pumice surfaces preferentially removed high UV-absorbing fractions of NOM, with UV absorbance reductions up to 90%. Control experiments indicated that iron oxide species bound on pumice surfaces are stable, and potential iron release to the solution is not a concern at pH values of typical natural waters. Based on high NOM adsorption capacities, iron oxide coated pumice may be a promising novel adsorbent in removing NOM from waters. Furthermore, due to preferential removal of high UV-absorbing NOM fractions, iron oxide coated pumice may also be effective in controlling the formation of disinfection by-products in drinking water treatment.     

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).     

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。     

超声波／零价铁降解水中双酚A

研究了超声波／零价铁（US／Fe^0）工艺对水中双酚A（BPA）的降解效果及影响因素。结果表明,US／Fe^0工艺可以有效降解水中的BPA,具有协同作用,且降解过程符合一级动力学规律;Fe^0具有促进和抑制的双重作用;超声功率越大,越有利于BPA的降解;初始浓度较低时,BPA的降解效果较好;弱酸性条件有利于BPA的降解;加入一定量的自由基捕获剂（正丁醇）可以抑制BPA的降解;联合作用2h后,TOC的去除率较低,说明其矿化程度不完全。     

有机配体对纳米零价铁还原硝基苯的影响与机理

通过FeSO4·7H2O与NaBH4反应,采用液相还原法制备纳米级零价铁(NZVI),并用XRD,SEM对其性能进行表征。研究了纳米零价铁还原硝基苯(NB)的动力学规律及柠檬酸、草酸、柠檬酸钠、草酸钠、乙二胺四乙酸二钠(EDTA二钠盐)几种有机小分子对其还原效率的影响,并对其机理进行了初步探讨。结果表明,纳米零价铁去除硝基苯反应符合准一级动力学方程,并且当硝基苯浓度一定时,增加NZVI投加量,去除率会显著增大;当NZVI浓度一定时,硝基苯浓度越低,去除率越高;柠檬酸和EDTA二钠盐在较低浓度时抑制还原反应进行,而在3 mmol/L左右时,具有促进还原反应进行的作用,而草酸、柠檬酸钠和草酸钠则为抑制作用。