修复硝基苯污染底泥的活性覆盖材料筛选

针对硝基苯污染底泥修复的活性覆盖技术,筛选了适合阻断底泥中硝基苯释放的还原剂和吸附剂.采用的零价铁可迅速将难生物降解的硝基苯还原为苯胺,提高其生物可降解性,有利于将污染物彻底去除.零价铁对硝基苯的还原反应速率随着零价铁剂量的提高而提高,反应速率常数≥>10.001 min~(-1).吸附试验结果表明,在煤渣、活性炭、焦炭以及硅藻土几种常见的吸附剂中,活性炭具有最佳的吸附能力,但是其价格昂贵,不适于大规模应用.而廉价易得的煤渣对硝基苯及其降解产物苯胺具有良好的吸附性能,对硝基苯和苯胺的最大理论吸附量达到924.9 mg·kg~(-1)和1692.2 mg·kg~(-1).因此提出以煤渣为吸附基质,并添加一定比例零价铁的复合活性覆盖材料,为硝基苯污染底泥修复提供一种新的方向和基本参数.     

硝基苯厌氧降解过程中Fe0的促进作用

尝试在硝基苯生物厌氧降解过程中,添加零价铁实现电子催化与生物代谢的协同作用,结果发现零价铁能够促进硝基苯的厌氧转化并主要生成苯胺,初始浓度为240.00mg·l-1的硝基苯废水,当厌氧微生物浓度为5000.00mg·l-1左右时,在2L的试验液中,当零价铁投加量由0.50g增加到5.00g时,硝基苯的转化率和苯胺的产生量急剧增加;零价铁的投加量为5.00g时与不加零价铁相比,硝基苯的转化率提高了2.43倍,苯胺的生成量提高了2.12倍;通过设计Fe0,Fe2 ,Fe3 及Fe3O4的对比实验,证明零价铁的作用主要表现为其腐蚀形成Fe2 的过程为硝基苯的厌氧生物转化提供了电子以及该过程中生成的Fe2 和Fe3 的生物营养作用.     

土壤中取代硝基苯化合物被零价铁还原的机理

以气相色谱-质谱联用仪(GC-MS)分析和密度泛函理论(DFT)计算,探讨了土壤中甲基、氯代硝基苯混合物在常温常压下被零价铁还原的机理.GC-MS数据证明,取代硝基苯在土壤中被零价铁还原的主要产物是苯胺,同时还检测到微量的亚硝基苯、甲基苯二氮烯(对二甲基偶氮苯)、氯苯二氮烯(对二氯偶氮苯)等分解和缩合中间产物.理论计算表明:随还原程度的加深,对硝基甲苯和对氯硝基苯反应体系的能量从高到低,还原反应通过逐步添加质子和电子到硝基而进行,质子亲和力、电子亲和力起主导作用.逐步还原的机理合理地解释了实验中还原反应对土壤pH值的敏感以及微量中间产物的生成过程.苯环上的氯或甲基对还原反应的影响没有明显的差异.     

中性条件下超声波/零价铁协同降解活性艳红X-3B

考察了中性条件下超声波降解、零价铁还原及超声波-零价铁联用对活性艳红X-3B模拟废水的降解效果,通过对比降解过程中UV-Vis光谱的变化,探讨了超声波-零价铁协同处理活性艳红X-3B的可行性.结果表明,在中性条件下超声波对活性艳红X-3B降解缓慢,经过25min辐射后,活性艳红X-3B的分解率不足7.5%;零价铁直接还原速率较慢,反应25min后,活性艳红X-3B的分解率仅为48.82%;"超声波/零价铁"对降解活性艳红X-3B有明显的协同效应,25min后分解率达99.42%(600W),反应符合准一级动力学过程.与零价铁直接还原相比,在200W,400W和600W超声波的协同作用下,X-3B降解的表观反应速率常数分别提高了2.12,2.76和4.00倍,半衰期相应缩短.另外,添加H2O2会抑制协同效应.     

零价铁还原和过硫酸盐氧化联合降解水中硝基苯

将零价铁(Fe0)的还原和过硫酸盐(persulfate,PS)的高级氧化技术结合用于水中难降解有机污染物硝基苯的去除.研究结果表明,Fe0在常温常压下可将硝基苯还原生成苯胺,随着Fe0投加量的增加,硝基苯还原为苯胺的速率逐渐增大.PS本身对硝基苯氧化作用不明显,但在Fe0与PS二者联合体系中,硝基苯和苯胺同时被去除,而且随着PS投加量的增加二者被去除的速度也随之增加.在Fe0还原和PS氧化联合处理硝基苯的体系中可能存在两个过程,一是Fe0还原硝基苯产生苯胺和二价铁离子Fe2+,二是Fe2+催化PS产生强氧化性的硫酸根自由基将苯胺氧化降解.     

Fe~0对土壤中3-硝基甲苯的还原作用

研究常温常压下零价铁(ZVI或Fe0)对土壤中3-硝基甲苯(MNT)的还原作用.结果表明:零价铁能够有效地将土壤中的MNT还原为3-甲基苯胺.在MNT为2.5×10-6mol·-1,铁粉加入量为25mg·g-1,土壤初始pH值为6.8,含水量为75%,温度为25℃的条件下,反应5h后MNT的还原率可达95%.随着体系反应时间的延长,温度的升高,土壤含水量的增大和铁粉用量的增加,MNT的还原率均增大.将土壤初始pH值控制在偏酸性有利于反应的进行.     

Fe^0对土壤中对氯硝基苯和对硝基甲苯的还原

采用零价铁(Fe0)还原技术,在25℃和常压下修复受对氯硝基苯(PCNB)和对硝基甲苯(PNT)混合污染的土壤,研究不同反应条件对还原反应的影响及产物在反应历程中的变化.实验结果表明:零价铁能够有效地将土壤中PCNB和PNT还原为其对应的苯胺化合物.在PCNB和PNT的初始含量约为2.5×106mol·g-1,Fe0加人最为25 mg·g-1,土壤水分含量为0.75 mL·g-1,土壤初始pH值为6.8,于25℃下反应5 h,PCNB和PNT的还原率都可达93%以上.Fe0用量、土壤初始pH值、温度和土壤含水量均对Fe0还原硝基苯类化合物有较明显影响,偏酸性的土壤、较高的温度、增加Fe0用量和饱和的土壤含水量能显著提高还原率.     

零价铁协同超声波降解2,3,4,6-四氯酚的特性

研究了2,3,4,6-四氯酚(TeCP)在超声波/零价铁协同体系中的降解,结果表明,拟一级动力学能很好的拟合降解过程,协同体系中TeCP一级降解速率常数为0.0141min~(-1),为同等条件下零价铁体系降解速率常数的10.07倍,且大于两者之和,说明两者之间存在明显协同效应;零价铁(Fe~0)投加量、初始pH值、初始TeCP浓度(C_0)、超声功率和溶液离子强度等控制参数对TeCP降解速率的影响表明,其拟一级速率常数在Fe~0量为2g·l~(-1),初始pH值为6.0,离子强度0.8mol·l~(-1)Na_2SO_4以及超声功率350W时达最大值,并随着C_0的升高而降低.     

强化的零价铁PRB技术对PCBs污染地下水的修复

本实验强化了零价铁可渗透反应墙（Permeable Reactive Barrier,PRB）技术,分别用还原铁粉、还原铁粉＋锌粉、还原铁粉＋活性炭为主要的反应介质,以Arcolor1242为靶污染物,对强化的零价铁PRB技术治理多氯联苯污染的地下水的可行性和有效性进行了模拟研究。实验结果表明：在温度10℃,有效孔隙率为61%~67%,水的渗透速度为0.7~0.8 m.d-1的条件下,3个反应柱稳定期对PCBs的去除率分别达到94%、85%、79%,pH值从6.87升高到8.78、10.2、7.93;氧化还原电位从-48.6 mV降到-135、-107、-86.4 mV;出水铁离子的平均质量浓度为0.241、0.129和0.201 mg.L-1,脱氯率平均值为49.6%、72.6%、58.6%。综合考虑处理效果与成本,用零价铁PRB技术治理PCBs污染的地下水是可行的。     

零价铁对土壤中4-氯苯酚还原脱氯研究

氯苯酚是常见的环境污染物，它们在土壤中的加速分解可以减少对人类健康的危害。以恒温培养为方法，GC-MS为检测手段，研究了在常温常压下土壤中4-氯苯酚(4-CP)在零价铁作用下的还原脱氯反应。结果表明：4-CP可以被来自零价铁的电子还原，零价铁能够有效促进土壤中的4-CP脱除苯环上的氯原子，从而达到降低毒性、增加可生化性目的。反应条件如初始pH、时间、零价铁用量等均对4-CP还原脱氯效率有重要影响，特别是当初始pH值控制在偏酸时更有利于反应的进行。在零价铁加入量500mg、初始pH=4、反应时间7d的条件下，零价铁对土壤中4-CP还原脱氯效率最高可以达到65％。利用实验数据，对零价铁作用下4-CP还原脱氯的反应机理也进行了初步探讨。     

Nanoscale zero-valent iron supported on biochar for the highly efficient removal of nitrobenzene

• Biochar supported nanoscale zero-valent iron composite (nZVI/BC) was synthesized. • nZVI/BC quickly and efficiently removed nitrobenzene (NB) in solution. • NB removal by nZVI/BC involves simultaneous adsorption and reduction mechanism. • nZVI/BC exhibited better catalytic activity, stability and durability than nZVI. The application of nanoscale zero-valent iron (nZVI) in the remediation of contaminated groundwater or wastewater is limited due to its lack of stability, easy aggregation and iron leaching. To address this issue, nZVI was distributed on oak sawdust-derived biochar (BC) to obtain the nZVI/BC composite for the highly efficient reduction of nitrobenzene (NB). nZVI, BC and nZVI/BC were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). For nZVI/BC, nZVI particles were uniformly dispersed on BC. nZVI/BC exhibited higher removal efficiency for NB than the simple summation of bare nZVI and BC. The removal mechanism was investigated through the analyses of UV-Visible spectra, mass balance and XPS. NB was quickly adsorbed on the surface of nZVI/BC, and then gradually reduced to aniline (AN), accompanied by the oxidation of nZVI to magnetite. The effects of several reaction parameters, e.g., NB concentration, reaction pH and nZVI/BC aging time, on the removal of NB were also studied. In addition to high reactivity, the loading of nZVI on biochar significantly alleviated Fe leaching and enhanced the durability of nZVI.     

Nitrobenzene contamination of groundwater in a petrochemical industry site

The contaminant transport distance is predicted using numerical model. Zero-valent iron can be used to effectively transform nitrobenzene to aniline. Experiment shows that two-layer PRB systems have a very good treatment effect. Organic contamination of groundwater is a major concern in China. However, remediation technology for groundwater contamination to address the potential harm and danger brought by the above-mentioned serious issue is still in the research stage. This study aims to improve the current research findings. In the research project, drilling, soil, and groundwater sampling and analysis were conducted in a contamination site of a petrochemical plant, migration of contaminants to the river was predicted using a numerical model, the sequence permeable reactive barrier (PRB) for treating nitrobenzene (NB) and benzene was proposed, and simulation was carried out. Research findings demonstrated that three leaking locations had been identified in the plant, the major pollutants were NB and benzene, and the groundwater contamination area was around 640000 m². Computation results of the numerical model indicated that, in the worst case, the groundwater plume would reach the river after migration for nearly 9 years, which would endanger the safety of surface water supply. Furthermore, the two-PRB system with the filling of zero-valent iron (ZVI) and granular activated carbon attached with biofilm exerted strong remediation effects. Experimental results indicated that ZVI could transform NB to aniline effectively with a rate of approximately 93%. Meanwhile, aniline, benzene, and other organic pollutants could easily be biodegraded.     

壳聚糖稳定纳米铁去除地表水中Cr(Ⅵ)污染的影响因素

以壳聚糖为稳定剂,制备纳米零价铁颗粒,TEM表征结果显示:其粒径分布范围为20—150 nm,平均粒径为82.4 nm.研究表明,壳聚糖稳定的纳米铁去除Cr(Ⅵ)的还原反应符合一级反应动力学方程.溶液中投加稳定剂壳聚糖,当壳聚糖浓度为150 mg.l-1时,80 min内表观一级动力学常数kobs约为空白溶液的2倍;干扰离子Ca2+,Mg2+,HCO3-和CO32-对壳聚糖稳定纳米铁去除Cr(Ⅵ)的批试验结果显示,Ca2+和Mg2+在80 min内使壳聚糖稳定纳米铁对Cr(Ⅵ)去除率分别降低了约20%和10%;HCO3-和CO32-的存在使去除率降低了约10%.     

Degradation of chlorinated phenols by nanoscale zero-valent iron

Chlorophenols (CPs), as important contaminants in groundwater, are toxic and difficult to biodegrade. Recently nanoscale zero-valent iron received a great deal of attention because of its excellent performance in treating recalcitrant compounds. In this study, nanoscale zero-valent iron particles were prepared using chemical reduction, and the reductive transformations of three kinds of chlorinated phenols (2-CP, 3-CP, and 4-CP) by nanoscale zero-valent iron under different conditions were investigated. The transformation process of the CPs was shown to be dechlorination first, then cleavage of the benzene ring. The removal efficiency of the CPs varied as follows: 2-CP > 3-CP > 4-CP. The reactivity of CPs was associated with their energy of lowest unoccupied molecular orbit (E _LUMO). With the increase in initial concentrations of CPs, removal efficiency decreased a little. But the quantities of CPs reduced increased evidently. Temperature had influence on not only the removal efficiency, but also the transformation pathway. At higher temperatures, dechlorination occurred prior to benzene ring cleavage. At lower temperatures, however, the oxidation product was formed more easily.     

纳米Fe0对Cr（VI）的还原及其影响因素

采用纳米Fe0还原水溶液中的Cr（Ⅵ）,考察纳米Fe0投加量、Cr（Ⅵ）初始浓度、溶液pH值和有机酸等因素对cr（Ⅵ）还原的影响。结果表明,纳米Fe。对Cr（Ⅵ）的还原效果明显,其对Cr（Ⅵ）的还原率分别是铁粉和铁屑的7和13倍。Cr（Ⅵ）溶液初始质量浓度为20mg·L-1、Fe。投加量为5g·L“条件下,反应24h时纳米Fe0对Cr（Ⅵ）的还原率达82．7％。溶液低pH值可以促进Fe。的腐蚀速度,提高反应速率,当pH值为3．0时还原效果最好。草酸、丙二酸和丁二酸对纳米Fe。还原Cr（Ⅵ）均有明显的促进作用,3种有机酸对Cr（Ⅵ）还原率的提高幅度由高到低依次为草酸、丙二酸和丁二酸。     

Sulfate reduction in groundwater: characterization and applications for remediation

Sulfate is ubiquitous in groundwater, with both natural and anthropogenic sources. Sulfate reduction reactions play a significant role in mediating redox conditions and biogeochemical processes for subsurface systems. They also serve as the basis for innovative in situ methods for groundwater remediation. An overview of sulfate reduction in subsurface environments is provided, along with a brief discussion of characterization methods and applications for addressing acid mine drainage. We then focus on two innovative, in situ methods for remediating sulfate-contaminated groundwater, the use of zero-valent iron and the addition of electron-donor substrates. The advantages and limitations associated with the methods are discussed, with examples of prior applications.     

Process control factors for continuous microbial perchlorate reduction in the presence of zero-valent iron

Process control parameters influencing microbial perchlorate reduction via a flow-through zero-valent iron （ZVI） column reactor were investigated in order to optimize perchlorate removal from water. Mixed perchlorate reducers were obtained from a wastewater treatment plant and inoculated into the reactor without further acclimation. Examined parameters included hydraulic residence time （HRT）, pH, nutrients requirement, and perchlorate reduction kinetics. The minimum HRT for the system was concluded to be 8 hr. The removal efficiency of 10 mg. L-1 influent perchlorate concentration was reduced by 20%-80% without control to the neutral pH （HRT = 8 hr）. Therefore pH was determined to be an important parameter for microbial perchlorate reduction. Furthermore, a viable alternative to pH buffer was discussed. The microbial perchlorate reduction followed the first order kinetics, with a rate constant （K） of 0.761 hr-1. The results from this study will contribute to the implementation of a safe, cost effective, and efficient system for perchlorate reduction to below regulated levels.     

零价铁对土壤中间氯硝基苯和间硝基甲苯的还原研究

常温常压下,利用零价铁(ZVI)对土壤中间氯硝基苯(MCNB)和间硝基甲苯(MNT)2类污染物进行了修复研究.结果表明:ZVI能有效将MCNB和MNT还原为相应的苯胺类化合物,无进一步脱氯或脱甲基反应发生.反应时间、土壤含水量、土壤初始pH值、ZVI用量和反应温度均对还原效果有较明显的影响,当土壤中2种污染物各自浓度约为2.5×10-6 mol·g-1,ZVI加入量为25 mg·g-1,土壤含水量为0.75 mL·g-1,初始pH值为6.8时,(25±1) ℃条件下反应5 h后,2种化合物的还原率均达到80%以上,较长的反应时间、偏酸性的土壤、较高的温度、ZVI用量的增加以及饱和的土壤含水量均能显著提高还原率.