细菌和颗粒浓度对纳米零价铁材料的柱迁移性影响

通过填充柱实验研究了氢自养反硝化细菌(HB)和不同颗粒浓度对纳米零价铁(nZVI)和壳聚糖包覆纳米零价铁(CS-nZVI)在多孔介质中迁移的影响。利用穿透曲线考察了纳米零价铁材料的迁移性能。结果表明,颗粒浓度(0.2,0.5,1 g/L)对nZVI在多孔介质中的迁移性没有显著影响;CS-nZVI在低浓度(0.2 g/L)下有较好的迁移性。CS-nZVI在不同颗粒浓度下的穿透率均高于nZVI,显示出较好的迁移性能。纳米零价铁悬浮液中加入细菌,颗粒迁移性增强,其中1/3 HB条件下对nZVI和CS-nZVI迁移的促进作用更明显;细菌存在条件下,nZVI迁移性能随颗粒浓度增加而增强,而CS-nZVI的迁移性与颗粒浓度不呈正相关关系。     

高分散性纳米铁的制备及其表征

以可生物降解的聚苯乙烯磺酸钠(PSS)为分散剂,制备了能稳定分散于水中的零价纳米铁(nZⅥ).未改性的零价纳米铁呈规则的球形或椭球形,平均粒径为60～80 nm,经PPS分散后的纳米铁nZVI/PSS则呈现微小的粒状分散在PSS中.pH=8时,与nZVI相比,nZVI/PSS的ζ电位由+9.4 mV降至-36.7 mV,同时等电点也由8.7变为小于5.XPS分析结果显示,nZVI和nZVI/PSS表面元素构成相同,但nZVI/PSS表面有零价铁存在,而nZVI表面则主要由铁的氧化物组成.实验结果表明,两种纳米铁对Cr(VI)的去除率非常接近,在纳米铁投加量为1.0g·L-1,Cr(VI)初始浓度为100 mg·L-1的条件下,Cr(VI)的去除率在10 min内均能达到95％,在30 min内能达99％,表明nZVI/PSS具有较高活性.     

羧甲基淀粉钠改性零价纳米铁在饱和多孔介质中的迁移

利用羧甲基淀粉钠(CMS-Na)对纳米零价铁(nZVI)进行改性。通过沉降实验,探讨改性剂添加量对纳米零价铁的分散性能的影响。利用柱实验多层位取样,来刻画饱和多孔介质中nZVI悬浮液迁移的过程,并分析其在改性剂添加量(nZVI、nZVI/200%CMS-Na、nZVI/400%CMS-Na)、初始流速(0.023 6,0.047 2,0.070 8 cm/s)、nZVI浓度(0.5,0.75,1 g/L)的条件下的迁移规律。结果表明,分散效果完全不与CMS-Na与nZVI的质量比成正比,nZVI/400%CMS-Na的分散效果最好,nZVI/500%CMS-Na的分散效果反而变差;随着时间的增加,nZVI由下端往上端迁移,nZVI出流浓度也随着时间增加,然后趋于稳定不变。nZVI的迁移能力与分散性能、流速、浓度呈正相关关系。     

羧甲基淀粉钠改性零价纳米铁在饱和多孔介质中的迁移

利用羧甲基淀粉钠(CMS-Na)对纳米零价铁(nZVI)进行改性。通过沉降实验,探讨改性剂添加量对纳米零价铁的分散性能的影响。利用柱实验多层位取样,来刻画饱和多孔介质中nZVI悬浮液迁移的过程,并分析其在改性剂添加量(nZVI、nZVI/200%CMS-Na、nZVI/400%CMS-Na)、初始流速(0.023 6,0.047 2,0.070 8 cm/s)、nZVI浓度(0.5,0.75,1 g/L)的条件下的迁移规律。结果表明,分散效果完全不与CMS-Na与nZVI的质量比成正比,nZVI/400%CMS-Na的分散效果最好,nZVI/500%CMS-Na的分散效果反而变差;随着时间的增加,nZVI由下端往上端迁移,nZVI出流浓度也随着时间增加,然后趋于稳定不变。nZVI的迁移能力与分散性能、流速、浓度呈正相关关系。     

羧甲基纤维素钠改性零价铁在石英砂中的迁移能力

利用羧甲基纤维素钠（CMC）对零价铁进行改性,通过Zeta电位、粒型粒度和沉降曲线的变化探讨改性剂添加量影响零价铁分散的机理,同时考察改性剂添加量、流速和多孔介质类型对零价铁迁移的影响。结果表明,CMC对零价铁的分散机理符合DLVO模型,静电空间位阻带来的势垒增加量与CMC添加量成正相关,能促进零价铁的分散;经500%CMC（CMC与零价铁的质量比）改性的零价铁分散性能最好,成颗粒状、吸光度在90 min下降31%。受零价铁与石英砂作用能、填充介质的吸附位点和剪切力的影响,零价铁的迁移能力随着CMC添加量的增多,填充介质粒径的增大和流速的增加而增强。     

纳米零价铁在地下水中迁移的影响因素

纳米零价铁(nZVI)因其对大范围污染物具有高反应性,且可以快速减少许多优先源区的污染物,而成为应用最广泛的纳米材料之一。为了有效地将nZVI输送到污染区域,要解决的关键问题是nZVI在地下水中的稳定性、移动性和寿命。目前,很多学者对nZVI迁移的影响因素进行了大量研究,包括纳米铁的性质、多孔介质的特性、地下水的流动特点、微生物的影响等。文章对这些影响因素加以总结,为进一步的研究提供了较为系统的参考。     

多孔材料负载型纳米零价铁的制备及其在环境中的应用进展

纳米零价铁(nZVI)因其比表面积大,还原电势高、反应活性优异等特点被广泛应用于地下水和废水污染物的去除,展现出良好的去除效果。但易团聚、易氧化等问题使nZVI的应用受到局限。近年来,通过将nZVI负载在多孔材料上来改善其局限、提高其应用潜能的理论和研究受到广泛关注。本文从制备方法,对污染物的去除能效,增效机制等方面对负载型纳米零价铁的相关研究做出总结。提出了目前纳米零价铁系材料应用过程中存在的问题,对负载型纳米零价铁的应用前景进行了展望。     

多孔炭材料改性纳米零价铁的研究进展

多孔炭材料因其特殊的孔隙结构、较好的化学稳定性及较强的导电性等特性,近年来通过多孔炭材料改性纳米零价铁（nZVI）解决易团聚、迁移距离小、反应性低等问题,成为提高nZVI原位修复污染场地作用效果的研究热点。本文阐述了介孔炭、石墨烯、碳纳米管3种碳材料的特性,分析了多孔炭材料负载对nZVI迁移率、反应活性、选择性和电催化性的影响机理,并结合目前实验室研究到实际污染测试场地的应用实例对改性nZVI未来方向进行展望,指出碳材料载体今后的研究热点是优化多孔炭材料的形貌、表面基团、掺杂其他原子等。     

纳米铁的绿色合成及其在环境中的应用研究进展

纳米铁（零价铁及铁氧化物）比表面积大、还原能力强、反应活性高，是一种良好的环境功能材料。传统的纳米铁合成方法中，物理方法对反应所需仪器设备要求较高，化学方法使用的还原剂具有毒性，绿色合成方法能够有效克服传统方法的不足之处。本文首先根据合成途径、纳米铁的类型介绍了利用植物和微生物对纳米零价铁（nZVI）及纳米铁氧化物（IONPs）进行绿色合成的方法，同时论述了制备的纳米铁所表现的特征（如形貌、尺寸、聚集倾向、等电位点）。随后总结了纳米铁通过不同反应机制（吸附、还原、催化氧化）去除环境有机、无机污染物（染料、芳香族化合物、硝酸盐、重金属）的应用。最后指出了纳米铁在绿色合成与实际应用过程中存在的挑战性问题及解决方法，以期为纳米铁今后的深入研究和大规模的工业生产应用提供参考依据。     

纳米零价铁的制备、改性及对废水中重金属和 有机污染物的去除

纳米零价铁（nZVI）结合了零价铁还原性强和纳米材料比表面积大的特点,能够高效去除水体中的重金属和有机污染物,是当前环境科学领域研究的热点之一。研究表明单一nZVI颗粒存在易团聚及表面易被氧化等问题,影响nZVI颗粒形态和对污染物去除效果,限制了其在环境修复中的应用。针对目前的研究现状,本文分析并总结了以下内容：①nZVI常用的制备方法;②提高nZVI活性与稳定性的改性方法,如合成时添加表面活性剂和负载材料;③nZVI去除废水中Cr、Cd、Cu和As等重金属和硝基苯、氯代芳烃、氯代脂肪烃等有机污染物的主要机理及影响因素;④应用于自然环境中的nZVI可能对环境产生的毒理学效应和在环境修复过程中存在的潜在风险及其评估;⑤对nZVI今后的研究重点和方向进行分析和展望。     

滤料表面电动电位的研究

根据流动电位与表面ξ电位的关系研制了一套测定滤料表面ζ电位的装置,经测定计算出了常用六种水处理滤料的表面ζ电位。结果表明:磁铁矿、沸石、石英砂、陶粒砂、核桃壳、无烟煤表面ζ电位分别为-60.85mV、-25.45mV、-24.37 mV、-21.49 mV、-14.24mV、-14.17mV。用红外光谱分析说明了各种滤料表面ζ电位存在差异的原理。     

滤料表面电位对滤床过滤效果的影响

滤床过滤工艺广泛应用于水处理领域，滤料表面电位对水中悬浮颗粒的过滤去除有很大的影响。石英砂滤料表面带较高的负电位，一些情况下不利于悬浮颗粒的去除。对石英砂、氧化铁改性滤料、复合改性滤料的表面电位和过滤效果的对比表明，复合改性滤料表面电位接近于中性，对水中的悬浮颗粒有稳定良好的去除效果。     

Modelling arsenic(III) adsorption from water by sulfate‐modified iron oxide‐coated sand (SMIOCS)

A medium developed by coating BaSO₄ and Fe on quartz sand known as sulfate‐modified iron oxide‐coated sand (SMIOCS) was evaluated for the removal of arsenic(III) from simulated water with an ionic strength of 0.01 M NaNO₃ during batch studies. The medium was characterised for BET surface area, alkali‐resistance, acid‐resistance and the presence of iron and barium on the coated surface. Two simplified kinetic models, ie active available site (AAS) and chemical reaction rate models, were tested to investigate the adsorption mechanisms. The values of rate constants for both the models were found to decrease with increasing As(III) concentrations in the solute. The inverse relationship of rate constants of the reaction rate model with BET surface area showed that As(III) adsorption on SMIOCS was not due to physisorption but to chemisorption. A study of the effect of solute temperature showed that the adsorption of As(III) on SMIOCS media was due to chemisorption. The results of isothermal studies conducted at different pH values showed that adsorption data satisfied both the Langmuir and the Freundlich isotherm models. The adsorption of As(III) on the medium was pH dependent and maximum removal was observed in the pH range of 7–9. © 2002 Society of Chemical Industry     

Immobilization of nano-zero-valent irons by carboxylated cellulose nanocrystals for wastewater remediation

Nano-zero-valent irons (nZVI) have shown great potential to function as universal and low-cost magnetic adsorbents. Yet, the rapid agglomeration and easy surface corrosion of nZVI in solution greatly hinders their overall applicability. Here, carboxylated cellulose nanocrystals (CCNC), widely available from renewable biomass resources, were prepared and applied for the immobilization of nZVI. In doing so, carboxylated cellulose nanocrystals supporting nano-zero-valent irons (CCNC-nZVI) were obtained via an in-situ growth method. The CCNC-nZVI were characterized and then evaluated for their performances in wastewater treatment. The results obtained show that nZVI nanoparticles could attach to the carboxyl and hydroxyl groups of CCNC, and well disperse on the CCNC surface with a size of ~10 nm. With the CCNC acting as corrosion inhibitors improving the reaction activity of nZVI, CCNC-nZVI exhibited an improved dispersion stability and electron utilization efficacy. The Pb(II) adsorption capacity of CCNC-nZVI reached 509.3 mg·g⁻¹ (298.15 K, pH= 4.0), significantly higher than that of CCNC. The adsorption was a spontaneous exothermic process and could be perfectly fitted by the pseudo-second-order kinetics model. This study may provide a novel and green method for immobilizing magnetic nanomaterials by using biomass-based resources to develop effective bio-adsorbents for wastewater decontamination.     

Transport and retention of polymer-stabilized zero-valent iron nanoparticles in saturated porous media: Effects of initial particle concentration and ionic strength

This study investigated the transport and retention of polyacrylic acid and polyvinylpyrrolidone stabilized zero-valent iron nanoparticles (PAA-ZVIN and PVP-ZVIN) in saturated porous media. The transport experiments were conducted in sand packed columns. The breakthrough curves (BTCs) and retention curves of ZVIN were analyzed. Results of transport experiments showed that increasing initial particle concentration and ionic strength led to a decrease in ZVIN transport. The zeta potentials and hydrodynamic diameters of PAA-ZVIN were apparently more negative compared to PVP-ZVIN. Results indicated that some mechanisms such as aggregation, ripening, and surface roughness had considerable impact on ZVIN retention in porous media.     

负载氧化铁石英砂用于Fenton-流化床体系处理印染废水的研究

制备了负载氧化铁石英砂催化载体,负载的氧化铁颗粒其粒径为100 nm左右。通过重复使用负载石英砂载体探讨其稳定性,结果表明,pH=3.0,H2O2初始浓度为10 mmol.L-1,催化剂载体投加量40 g.L-1的条件下,亚铁投加量减少到0.2 mmol.L-1时,100 min后对甲基橙溶液的脱色率为97.5%。同时,负载石英砂载体重复使用5次后脱色率仍高于70%。表明负载氧化铁石英砂用于Fenton-流化床体系是一种有应用潜力的高级氧化处理废水的反应体系。     

Assessment of aged biodegradable polymer‐coated nano‐zero‐valent iron for degradation of hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine (RDX)

BACKGROUND: This study reports on the effects of aging on suspension behavior of biodegradable polymer‐coated nano‐zero‐valent iron (nZVI) and its degradation rates of hexahydro‐1,3,5‐trinitro‐1,3,5‐triazine (RDX) under reductive conditions. The polymers investigated included guar gum, potato starch, alginic acid (AA), and carboxymethyl cellulose (CMC). Polymer coating was used to mitigate nZVI delivery hindrance for in situ treatment of RDX‐contaminated groundwater. RESULTS: The RDX degradation rates by bare nZVI and starch‐coated nZVI suspensions were least affected by aging although these suspensions exhibited the least favorable dispersion behavior. CMC, AA, and guar gum coating improved nZVI rates of degradation of RDX but these rates decreased upon aging. The best suspension stability upon aging was achieved by CMC and AA. Guar gum with loadings rates one order of magnitude lower than that of CMC and AA achieved good iron stabilization but significantly higher RDX degradation rates. CONCLUSION: It is demonstrated that both migration and reactivity of polymer‐stabilized nZVI should be explicitly evaluated over a long period before application in the field. Guar gum coated nZVI appeared best suited for in situ application because it maintained good suspension stability, with RDX degradation rates least affected by aging compared with the other polymers tested. © 2012 Society of Chemical Industry     

地下水人工补给过程中流速对多孔介质胶体堵塞的影响机理

通过一系列室内砂柱模拟实验,研究了流速对胶体在饱和多孔介质中滞留-迁移行为的影响;运用COMSOL软件模拟,拟合实验数据后得到表征胶体沉积的关键参数。结果表明：流速增大缩短了胶体在多孔介质中的滞留时间,并增强水动力拖拽力,导致介质对胶体的吸附量减少,有利于胶体的迁移;回灌时间的延续造成的多孔介质渗透系数降低,可通过瞬间增大流速使渗透系数在较短时间内恢复,然而随后形成新的吸附渗透性仍会降低。水源离子强度、介质粗糙度等因素会影响胶体迁移的流速效应。在相同条件下,吸附系数随着离子强度的增大而增加,随着流速的增大而增加。综合来看,离子强度的增加可抵消一部分水动力拖拽力的影响,提高胶体在多孔介质中滞留的概率;介质表面粗糙度的增加,可削弱水动力拖拽力作用,同时增加胶体与介质的吸附、沉积点位和接触面积,导致胶体易于在多孔介质中发生滞留并可能进一步导致介质堵塞。     

Characterization of the adsorption behavior of aqueous cadmium on nanozero-valent iron based on orthogonal experiment and surface complexation modeling

Polyvinylpyrrolidone K-30(PVP) was introduced into the preparation of nanozero-valent iron(n ZVI) and the traditional liquid-phase reduction was improved. The introduction of PVP simplified the traditional method.The n ZVI prepared with this new approach showed excellent surface characters and high performance on the removal of cadmium. TEM results showed that the aggregates of n ZVI can reach to several micrometers in length but less than 100 nm in diameter. The iron particles that were enclosed by a layer of oxide film that is less than10 nm, demonstrated that the n ZVI possesses a core–shell structure. BET results indicate that the specific surface area of the n ZVI was 20.3159 m~2g~(-1). A three factor and three level orthogonal experiment was employed to find out the dominant factor that affects the removal rate of cadmium by n ZVI. Based on the range values, the prominence order of each factor was: initial p H of the solution N initial concentration of cadmium N dosage of n ZVI, the range was 96.453, 3.294 and 1.747, respectively. A simulation was performed under the same condition and a same conclusion was derived, this consistence confirmed the validity of the conclusion that p H is the most significant factor that affects the adsorption efficiency.