磷酸化纳米铁去除水中Cd2+、Zn2+、Ni2+的比较

重金属污染已成为全球关注的环境问题,镉、镍和锌是工业生产中常见的重金属污染. 纳米零价铁是重金属污染控制的重要环境功能材料,其改性优化工作也备受关注. 本文采用液相还原法在制备过程中添加KH₂PO₄合成磷酸化纳米铁(phosphorylated nanoscale zero-valent iron,P-nZVI),考察了磷酸化对纳米铁去除Cd²⁺、Zn²⁺、Ni²⁺的效果的影响,评估了磷酸化对抗pH、干扰离子影响的效果,并结合XRD、SEM、S/TEM、XPS等表征手段比较了P-nZVI去除3种重金属的作用机制. 研究表明,P-nZVI对Cd²⁺、Zn²⁺的去除效率均显著优于纳米零价铁(nanoscale zero-valent iron,nZVI),分别为79.6％、90.6％. 吸附过程以P-nZVI表面磷酸基团的吸附为主,均可用准二级动力学描述. Ni²⁺的去除包括吸附和还原作用,加剧了铁芯腐蚀,使其去除效率达到92.6％. 因此,磷酸化修饰能通过累积零价铁表面负电荷以加速吸附过程;裂纹结构能降低金属离子跨越氧化铁层的阻碍,促进氧化还原,提高Fe⁰利用率.     

改性碳毡电极构建杂化膜电容去离子去除阴离子型染料的性能及机理

根据染料不过膜的特点,构建了新型杂化半膜膜电容去离子（MCDI）装置,首次利用MCDI对阴离子型染料进行去除. 将铁氧化物以不同铁碳质量比掺杂在碳毡(CF)中制备复合电极,通过扫描电子显微镜（SEM）、X射线衍射（XRD）和X射线光电子能谱（XPS）等多重手段表征电极材料的形貌、结构和化学组成等,表明铁氧化物的成功掺杂. 并根据循环伏安（CV）和电化学阻抗谱（EIS）证明铁氧化物掺杂比例为25%的改性材料CF-Fe(25%)具有最优的电化学性能. 对比CFs对阴离子型染料刚果红（congo red,CR）的去除效果,并探究电压、染料浓度和pH等参数对CR去除性能的影响,验证最佳条件下对其他阴离子型染料的去除效果. 结合自由基捕获实验阐述MCDI对阴离子型染料的降解机理. 得到在1.2 V电压,流速3 mL·min−1下,pH 7的进水环境中,对100 mg·L−1的CR、新胭脂红染料（new carmine,NC）和日落黄染料（sunset yellow FCF,SY FCF）在15 min内分别达到66.3%、61.6%和60.7%的去除率,且酸性环境有利于染料的去除. 新型杂化半膜MCDI装置可直接将离子型染料富集,后经阳极产生的高活性自由基（·OH）氧化降解、去除,铁氧化物的掺杂可增加电极反应活性位点,利于染料的吸附,并促进·OH的生成. ·OH是降解染料的主要作用力. 该方法去除效率高,同时避免了膜污染,为MCDI去除阴离子型染料方面提供科学依据.     

Fe2+EDTA溶液络合-铁还原脱除烟气中NO

提出了“Fe2 螯合剂络合-铁粉还原-酸吸收”回收法脱除烟气中NO的新工艺,重点研究了模拟烟气中O2体积分数对NO络合量的影响,以及铁粉用量、铁粉粒径、搅拌速度对NO脱除效率的影响,确定了最佳的铁粉脱氮工艺条件,并对铁粉和铁屑的脱氮效果进行了比较。结果表明,烟气中O2的体积分数从0%增加到4.2%,NO络合量下降90.2%;NO脱除效率随铁粉用量和反应器搅拌速度的增加而增加,随铁粉粒径的增加而降低;过程的最佳工艺参数为,铁粉用量0.8g,铁粉粒径≤0.077mm,搅拌速度900r·min-1,在此条件下,对O2体积分数为5%的模拟烟气在搅拌反应器中可取得90%以上的NO脱除效率;用铁粉在1台搅拌反应器中取得的NO脱除效率和用铁屑在2个鼓泡反应器串联时所取得的效率相当。     

含氯有机物非生物降解方法的最新研究进展

通过介绍目前国际上对含氯有机物的非生物降解方法的最新研究成果,包括零价金属还原、金属组合体系还原脱氯、含铁化合物还原降解、催化加氢还原以及机械化学方法等.分析了每种技术的具体应用和存在的问题以及这些处理方法的发展方向等.     

Microbiological characteristics in a zero-valent iron reactive barrier

Zero-valent iron (Fe⁰)-based permeable reactive barriertreatment has been generating great interest for passivegroundwater remediation, yet few studies have paid particularattention to the microbial activity and characteristics withinand in the vicinity of the Fe⁰-barrier matrix. The presentstudy was undertaken to evaluate the microbial population andcommunity composition in the reducing zone of influence byFe⁰ corrosion in the barrier at the Oak Ridge Y-12 Plantsite. Both phospholipid fatty acids and DNA analyses were usedto determine the total microbial population and microbialfunctional groups, including sulfate-reducing bacteria,denitrifying bacteria, and methanogens, in groundwater andsoil/iron core samples. A diverse microbial community wasidentified in the strongly reducing Fe⁰ environment despitea relatively high pH condition within the Fe⁰ barrier (up topH 10). In comparison with those found in the backgroundsoil/groundwater samples, the enhanced microbial populationranged from 1 to 3 orders of magnitude and appeared to increase from upgradient of the barrier to downgradient soil. Inaddition, microbial community composition appeared to change overtime, and the bacterial types of microorganismsincreased consistently as the barrier aged. DNA analysisindicated the presence of sulfate-reducing and denitrifyingbacteria in the barrier and its surrounding soil. However, theactivity of methanogens was found to be relatively low,presumably as a result of the competition by sulfate/metal-reducing bacteria and denitrifying bacteria because of the unlimited availability of sulfate and nitrate in the site groundwater. Results of this study provide evidenceof a diverse microbial population within and in the vicinity ofthe iron barrier, although the important roles of microbial activity, either beneficially or detrimentally, on the longevityand enduring efficiency of the Fe⁰ barriers are yet to be evaluated.     

A strategy for aromatic hydrocarbon bioremediation under anaerobic conditions and the impacts of ethanol: a microcosm study

Increased use of ethanol-blended gasoline (gasohol) and its potential release into the subsurface have spurred interest in studying the biodegradation of and interactions between ethanol and gasoline components such as benzene, toluene, ethylbenzene and xylene isomers (BTEX) in groundwater plumes. The preferred substrate status and the high biological oxygen demand (BOD) posed by ethanol and its biodegradation products suggests that anaerobic electron acceptors (EAs) will be required to support in situ bioremediation of BTEX. To develop a strategy for aromatic hydrocarbon bioremediation and to understand the impacts of ethanol on BTEX biodegradation under strictly anaerobic conditions, a microcosm experiment was conducted using pristine aquifer sand and groundwater obtained from Canadian Forces Base Borden, Canada. The initial electron accepter pool included nitrate, sulfate and/or ferric iron. The microcosms typically contained 400 g of sediment, 600 approximately 800 ml of groundwater, and with differing EAs added, and were run under anaerobic conditions. Ethanol was added to some at concentrations of 500 and 5000 mg/L. Trends for biodegradation of aromatic hydrocarbons for the Borden aquifer material were first developed in the absence of ethanol, The results showed that indigenous microorganisms could degrade all aromatic hydrocarbons (BTEX and trimethylbenzene isomers-TMB) under nitrate- and ferric iron-combined conditions, but not under sulfate-reducing conditions. Toluene, ethylbenzene and m/p-xylene were biodegraded under denitrifying conditions. However, the persistence of benzene indicated that enhancing denitrification alone was insufficient. Both benzene and o-xylene biodegraded significantly under iron-reducing conditions, but only after denitrification had removed other aromatics. For the trimethylbenzene isomers, 1,3,5-TMB biodegradation was found under denitrifying and then iron-reducing conditions. Biodegradation of 1,2,3-TMB or 1,2,4-TMB was slower under iron-reducing conditions. This study suggests that addition of excess ferric iron combined with limited nitrate has promise for in situ bioremediation of BTEX and TMB in the Borden aquifer and possibly for other sites contaminated by hydrocarbons. This study is the first to report 1,2,3-TMB biodegradation under strictly anaerobic condition. With the addition of 500 mg/L ethanol but without EA addition, ethanol and its main intermediate, acetate, were quickly biodegraded within 41 d with methane as a major product. Ethanol initially present at 5000 mg/L without EA addition declined slowly with the persistence of unidentified volatile fatty acids, likely propionate and butyrate, but less methane. In contrast, all ethanol disappeared with repeated additions of either nitrate or ferric iron, but acetate and unidentified intermediates persisted under iron-enhanced conditions. With the addition of 500 mg/L ethanol and nitrate, only minor toluene biodegradation was observed under denitrifying conditions and only after ethanol and acetate were utilized. The higher ethanol concentration (5000 mg/L) essentially shut down BTEX biodegradation likely due to high EA demand provided by ethanol and its intermediates. The negative findings for anaerobic BTEX biodegradation in the presence of ethanol and/or its biodegradation products are in contrast to recent research reported by Da Silva et al. [Da Silva, M.L.B., Ruiz-Aguilar, G.M.L., Alvarez, P.J.J., 2005. Enhanced anaerobic biodegradation of BTEX-ethanol mixtures in aquifer columns amended with sulfate, chelated ferric iron or nitrate. Biodegradation. 16, 105-114]. Our results suggest that the apparent conservation of high residual labile carbon as biodegradation products such as acetate makes natural attenuation of aromatics less effective, and makes subsequent addition of EAs to promote in situ BTEX biodegradation problematic.     

纳米零价铁对铀尾矿库土壤中铀形态分布及固定效果的影响

针对纳米零价铁(nZVI)对铀尾矿库土壤中铀形态分布和U(Ⅵ)固定效果影响问题,采用逐级化学提取、毒性浸出(TCLP)和磁性分离实验,利用SEM-EDS和XRD对nZVI固定前后的铀尾矿土壤进行表征;研究了nZVI在不同投加量和pH条件下,对尾矿库土壤固定前后铀的形态分布和固定效果的影响,并对nZVI的固定机理进行了探讨。结果表明：当nZVI的投加量为8%、pH为5时,土壤中U(Ⅵ)的固定效果最好,固定后土壤中铀的毒性浸出值仅为13.98%;对经过nZVI处理后的铀尾矿土壤进行磁性分离发现,磁性和非磁性土壤重量占比分别为32.87%和67.13%,其铀含量分别达到55.05%和44.95%,说明nZVI对土壤中的U(Ⅵ)有较好的富集作用。nZVI对铀尾矿库土壤中的U(Ⅵ)有较好的原位固定和富集效果,并能减少土壤中铀的析出。     

混气悬浮磁化焙烧铁尾矿及其磁分选效果

为实现铁尾矿资源化回收利用,以H₂、CO、CO₂和N₂模拟还原混气对铁尾矿进行悬浮磁化焙烧,通过磁选获得铁精矿。探究温度、时间、H₂和CO占比对铁精矿铁品位和回收率的影响,采用X射线衍射、振动样品强磁计、X射线光电子能谱、BET表面分析和扫描电子显微镜X光微区分析方法,探究悬浮磁化焙烧磁选过程中晶相结构变化和反应机理。结果表明,铁尾矿在温度、时间和H₂∶CO∶CO₂∶N₂（体积比）分别为600 ℃、10 min和20∶15∶15∶50时,铁精矿铁品位和回收率最优分别为62.06%和98.03%。铁精矿饱和磁化强度由0.77 Am²·kg⁻¹提升到59.43 Am²·kg^-1。悬浮磁化焙烧能有效将赤铁矿针铁矿还原为磁铁矿,且BET表面积提升了13.1676 m²·g⁻¹,并能通过磁选有效分离Fe₃O₄和SiO₂等脉石。本研究可为从铁尾矿中回收铁资源提供参考。     

焦炭和废铁屑微电解预处理垃圾渗滤液的研究

研究表明,废铁屑和焦炭微电解是预处理垃圾渗滤液的一种有效方法,可去除垃圾渗滤液COD、色度和腐殖酸等污染物质,改善其可生化性、降低负荷,为后续生化处理创造良好的条件.通过静态正交实验确定废铁屑和焦炭最佳投加体积比为1∶3;最佳反应pH值为4;动态实验中,反应时间为1 h时,COD和色度去除率分别高达68%和91%;BOD/COD从0.3提高到0.5左右.