利用扫描电镜技术研究纳米Ni-Fe颗粒对四氯化碳快速脱氯的机理

纳米铁具有高的比表面积和高反应活性,能快速将氯代烯烃还原成无毒氯离子、乙烯和乙烷,但对于氯代烷烃的脱氯仍能产生大量的氯代中间或最终产物,可以通过合成制得纳米双金属提高脱氯速率和减少氯代中间产物。本文利用扫描电镜测得实验室制备的纳米Ni-Fe(2%,质量分数)颗粒直径为20~60 nm,通过批实验方式对纳米Ni-Fe降解四氯化碳的反应动力学性质、产物、持久性能和反应机理进行了探讨。结果表明,纳米Ni-Fe体系主要最终产物为42%CH4和17%CH2Cl2。与铸铁屑和纳米铁相比,纳米Ni-Fe由于催化脱氯加氢,显著提高了氯代烃脱氯速率,同时降低了有毒氯代产物的产量,且Ni作为催化剂不会进入水体引起二次污染。纳米Ni-Fe颗粒在空气中具有很好的稳定性,虽然降解四氯化碳的最终产物CH4与纳米Pd-Fe相比少13%,但由于价格便宜,有望在工程上应用于氯代有机化合物水土污染治理。     

有机氯农药的零价铁脱氯降解研究进展

结合氯代有机物的零价铁脱氯降解研究进展,综述了国内外在零价铁脱氯降解有机氯农药领域的研究情况,大多研究表明零价铁降解有机氯农药的反应符合准一级反应动力学方程,普遍认同氢解反应机理但尚有争议,研究降解过程需考虑溶液pH值和铁表面活性作用的影响,尤其是铁表面的吸附作用不可忽略。最后提出了该技术存在的一些值得思考的问题,探讨了该研究领域的发展前景。     

水资源中氯代烃污染物的去除方法

随着工业化的发展。氯代有机溶剂使用越来越广泛。并且难于去除。在20世纪90年代初期，人们就已认识到用Fe^0恢复污染的地下水的潜力。国外正在研究帮使用扔几种还原挥发性氯代烃的还原反应介质，尤其要提高的是双金属反应系统，反应速度快，而且脱Cl中国难解产物少，目前国也只停留在实验室研究阶段，个别做了地上反应器的验证实验，它的脱Cl机理、介质钝化和完全脱Cl问题还有待于进一步研究。     

纳米镍/铁去除氯代烃影响因素的探讨

氯代烃是地下水中最常检出的有机污染物之一,传统的处理方法去除率很低。近年来随着铁还原技术的发展,纳米铁和纳米双金属也成为一个活跃的研究领域。利用批实验的研究方法以四氯乙烯(PCE)和四氯化碳(CT)为目标污染物,研究纳米镍/铁在去除PCE过程中的影响因素。实验结果表明,在碱性条件下,纳米Ni/Fe对PCE脱氯速率比在酸性和中性条件下脱氯速率更快;纳米Ni/Fe对初始浓度为6·51mg/L的PCE溶液脱氯速率是对初始浓度为20·56mg/L的PCE溶液脱氯速率的1·8倍;对于氯代程度相同的CT和PCE,对CT的脱氯速率明显快于对PCE。     

氯代有机物的降解研究

对含氯类有机物的降解进行研究,提出,氯代烷烃的降解主要采用双金属体系法;氯代芳香烃的降解多采用光催化氧化法;对于氯代酚类则采用催化臭氧氧化法、超声波降解法等.     

纳米镍/铁去除四氯乙烯的影响因素

氯代烃是地下水中最常检出的有机污染物之一,传统的处理方法需要很长时间与经费。近年来随着铁还原技术的发展,纳米铁和纳米双金属也是一个活跃的研究领域。本文利用批实验的研究方法以四氯乙烯(PCE)为目标污染物,研究纳米镍/铁在去除PCE过程中的影响因素。实验结果表明,暴露后的纳米Ni/Fe脱氯速率比不暴露时速率降低约4倍;反应温度是影响反应速率的一个重要因素之一,每升高10℃,反应速率常数kSA提高2~3倍;在一定范围内,Ni/Fe质量比越高,越利于脱氯反应的快速进行,当Ni/Fe的质量百分比为8%左右时,对氯代烃脱氯速率最快;反应液中的溶解…     

壳聚糖包覆纳米铁镍双金属的迁移性能及其降解地下水中三氯乙烯的研究

地下水中三氯乙烯(TCE)严重威胁公众健康和环境安全,纳米零价铁原位注射技术可以还原降解TCE,但是应用中,纳米零价铁存在易氧化团聚而失活、迁移性差等问题。为此,利用天然高分子壳聚糖作包覆剂增强分散性和稳定性,镍作催化剂增强反应活性,成功制备获得壳聚糖包覆纳米铁镍双金属颗粒(CS Fe Ni)。沉降光谱实验表明包覆壳聚糖后纳米铁的分散稳定性得到增强,Zeta电位测试进一步证实颗粒表面负电荷增加,提高了静电排斥力,使得CS Fe Ni分散稳定性明显改善。柱迁移实验表明改性后的CS Fe Ni迁移能力得到提高。批实验表明CS Fe Ni能够高效降解TCE并能完全脱氯,研究结果为纳米铁原位注射技术的实际应用提供了理论基础和实验参考。     

纳米铁还原脱氮动力学及其影响因素

饮用水中硝酸盐(NO3-)对人体健康有危害。为了去除水溶液中NO3-,在实验室制得纳米铁颗粒。它的粒径为20～40 nm,比表面积(BET)为49.16 m2/g。本研究通过批实验考察了纳米铁对NO3-还原脱氮动力学性质和影响NO3-脱氮快慢的主要因素,如反应pH、纳米铁投加量和NO3-起始浓度。实验结果表明,pH越低越有利于NO 3-还原。在一定范围内,NO 3-还原速率随纳米铁投加量增加而增大,而随NO 3-起始浓度升高而降低,反应遵循准一级反应动力学方程,表面吸附和氧化还原反应是纳米铁对NO3-脱氮的主要去除机理。纳米铁对NO3-还原过程中可能反应的途径进行了讨论,NO3-还原产物取决于反应条件。在本研究条件下,纳米铁对NO3-脱氮的最终产物主要为NH4+-N而不是N2,必须进行更多的研究来解决这一问题。     

纳米镍-铁去除四氯乙烯的影响因素

氯代烃是地下水中最常检出的有机污染物之一,传统的处理方法需要很长时间与大量经费。本文利用批实验的研究方法以四氯乙烯(PCE)为目标污染物,研究纳米镍铁在去除PCE过程中的影响因素。实验结果表明,暴露后的纳米镍铁脱氯速率比不暴露时速率降低约4倍;反应温度是影响反应速率的重要因素之一,每升高10℃,反应速率常数kSA提高2～3倍;在一定范围内,镍/铁质量比越高,越利于脱氯反应的快速进行,镍/铁的质量比为8%左右时,对氯代烃脱氯速率最快;反应液中的溶解氧不利于纳米颗粒对氯代烃的降解。     

基于SEM-EDS及GC-MS技术研究有机氯分子结构对零价铜脱氯机制的影响

零价铜作为一种廉价金属很少应用于促进氯代有机物脱氯研究,其原因是零价铜的催化还原脱氯活性差,且反应机制复杂。本文采用机械球磨技术制备了Cu-Fe和Cu-Ni合金,研究零价铜在不同微观环境下对对氯苯酚(4-CP)的脱氯行为,旨在考察有机氯分子结构对零价铜脱氯机制的影响。应用扫描电镜-能谱(SEM-EDS)及色相色谱-质谱(GC-MS)分析发现,铜原子的微环境及有机氯分子结构均影响铜的脱氯机制。在Cu-Fe体系中,Cu遵循经典的催化加氢脱氯机制,4-CP的降解产物为苯酚;Cu-Ni体系的还原作用来源于零价铜,其中的镍金属并未起到催化加氢作用,Cu-Ni合金及单独零价铜对4-CP的降解产物是环己酮。零价铜对4-CP的降解率可达70%以上,而Cu-Fe体系的降解率仅为34%,两者对芳香族氯代物的降解效率差距显著。零价铜能够降解化学稳定性高的4-CP和苯酚,但不能降解化学稳定性相对较差的脂肪族氯代有机物(如一氯乙酸和二氯乙酸),因此认为零价铜脱氯机制并非传统的催化加氢机制,而是遵循直接电子传递还原机制,且有机氯分子的苯环结构是零价铜直接电子传递还原的诱因。     

影响铁渗透反应格栅修复地下水中氯代烃长期运行性能的研究进展

铁渗透反应格栅技术修复地下水中氯代烃,尤其是四氯乙烯和三氯乙烯,已日臻成熟;近年,研究者对该技术的关注已集中到影响格栅长期运行性能的因素上。文章从地下水的常量化学组分、铁表面形成的矿物沉淀、铁渗透反应格栅中的微生物和共存有机污染物4个方面,对影响其长期运行性能的因素进行了综述。分析表明,铁表面矿物的长期积累是降低格栅长期运行性能的主要因素,并对该技术的发展进行了展望。     

Organic Contamination of Soil and Goundwater in the Piedimont Plain of the Taihang Mountains

The risk of groundwater contamination following the infiltration of waste surface water, is of great interest, particularly in areas experiencing water shortage. In this study, the distribution characteristics of contaminants along the Cihe River, in the piedimont plain of the Taihang Mountains, China, was investigated by measuring the soil and water samples. The main organic contaminants detected in different media include hydrocarbons, chlorinated hydrocarbons, polycyclic aromatic hydrocarbons, and pesticides. The main contaminants found in different media are mostly derived from the river water, which can be seen from the results of waste water from the river and groundwater, from the soil samples from different depth and distance of the profiles along the river. The distribution characteristics showed that there has been a natural attenuation of the contaminants from the river during their transportation through the soils and groundwater. The sorption of organic compounds to soil organic matter is thought to be a main mechanism of natural attenuation.     

Clamshell excavation of a permeable reactive barrier

Nowadays, permeable reactive barriers (PRB) are one of the most widespread techniques for the remediation of contaminated aquifers. Over the past 10 years, the use of iron-based PRBs has evolved from innovative to accepted standard practice for the treatment of a variety of groundwater contaminants (ITRC in: Permeable reactive barriers: lessons learned/new directions. The Interstate Technology and Regulatory Council, Permeable Reactive Barriers Team 2005). Although, a variety of excavation methods have been developed, backhoe excavators are often used for the construction of PRBs. The aim of this study is to describe the emplacement of a full-scale PRB and the benefits deriving from the use of a crawler crane equipped with a hydraulic grab (also known as clamshell excavator) in the excavation phases. The studied PRB was designed to remediate a chlorinated hydrocarbons plume at an old industrial landfill site, in Avigliana, near the city of Torino, in Italy. The continuous reactive barrier was designed to be 120 m long, 13 m deep, and 0.6 m thick. The installation of the barrier was accomplished using a clamshell for the excavation of the trench and a guar-gum slurry to support the walls. The performance of this technique was outstanding and allowed the installation of the PRB in 7 days. The degree of precision of the excavation was very high because of the intrinsic characteristics of this excavation tool and of the use of a concrete curb to guide the hydraulic grab. Moreover, the adopted technique permitted a saving of bioslurry thus minimizing the amount of biocide required.     

NOAA gulf of Mexico status and trends program: Trace organic contaminant distribution in sediments and oysters

Polynuclear aromatic hydrocarbons (PAH), chlorinated pesticides, and polychlorinated biphenyls (PCB) concentrations were determined in sediment and oysters to provide information on the current status of the concentration of these contaminants in Gulf of Mexico coastal areas removed from point sources of input. Coprostanol analyses of sediments showed that anthropogenic materials are associated with the sediments at all 153 stations sampled. The levels of contaminants encountered are low compared with areas of known contamination. Average PAH concentrations are nearly the same in oysters and sediments, although the molecular weight distribution is different. Average DDT and PCB concentrations are higher by a factor of 10 to 130 in oysters as compared to sediments. Continued sampling and analyses will allow for long-term trends in the concentrations of these contaminants to be determined.     

中国典型有机污染场地土层岩性和污染物特征分析

目前我国存在大量待修复场地,其分布具有一定的规律性和区域性,场地地层系统结构复杂、渗透性空间异质性显著,污染物种类复杂。总结场地典型土层结构和典型污染物有助于有针对性地开展修复技术的研发。为此,本文收集并整理了全国136处有机污染场地相关资料,对其地域性、地层及污染物特征总结如下:目前我国已经开展调查与修复的有机污染场地主要集中在京津冀和沪宁杭地区;有机污染场地土层基本都含有黏土等低渗透介质,而且都具有非均质性,其中67%场地土层有强非均质性;沪宁杭地区场地土层渗透性总体低于京津冀和辽中南地区,此外我国京津冀和辽中南地区场地调查深度(20.3 m)总体大于沪宁杭地区(12.8 m);我国有机污染场地地下水中最常见的有机污染物种类为氯代溶剂,依次为氯代烷烃类(场地数量占比84%)、氯代苯类(场地数量占比46%)和氯代烯烃类(场地数量占比33%);最常见的3种氯代溶剂依次为二氯乙烷、一氯苯和三氯甲烷。     

A field trial for in-situ bioremediation of 1,2-DCA

Historic spillages of chlorinated hydrocarbons at a vinyl chloride plant in the Rotterdam Botlek area in The Netherlands have lead to contamination of the underlying aquifer. The principal contaminant is 1,2-dichloroethane (1,2-DCA). The contamination is temporarily contained by a pump-and-treat system. A field trial was carried out to investigate the feasibility of treating the dissolved phase of 1,2-DCA via reductive dechlorination by injection of an aqueous solution of methanol, ammonium chloride and sodium chloride into the confined aquifer using an array of eight boreholes. Biodegradation of 1,2-DCA was localised. This was attributed to limited mixing of the carbon substrate within the test zone. In addition, clogging of recharge wells complicated groundwater circulation.     

地下水微量有机污染

在简要评述其污染特征与研究特点的基础上，总结介绍了地下水微量有机污染的分布，污染物种类、性质、危害和来源，有机物的物化特征及其在环境中的迁移转化，以及污染控制技术。非极性难溶挥发性有机物（ＶＯＣ＇ｓ）是地下水中危害最大而又最为常见的有机污染物，主要由氯代脂肪烃（ＣＨＣ）和单环芳香烃（ＢＴＥＸ）构成。多数水溶相ＶＯＣ＇ｓ不易被吸附，在地下环境具有很强的迁移性，但在适当条件下可生物降解。非水溶相ＣＨＣ常在地下水中积聚潜伏于含水层底板，迁移不受地下水流向的控制；非水溶相ＢＴＥＸ则漂浮于地下水表面。非水溶相ＶＯＣ＇ｓ很难产生生物降解。ＶＯＣ＇ｓ的去除过程复杂，许多领域有待探索。     

Contamination of groundwater by arsenic and other constituents in an industrial complex

This study examined the natural and anthropogenic pollution of groundwater at a national groundwater monitoring station (NGMS) in a dyeing industry complex, Korea. The arsenic contamination of a shallow well at the NGMS was noticed, starting from 22 months after the well installation. Possibilities of several mechanisms for As pollution of the groundwater were examined. The arsenical pyrite oxidation as a source mechanism in the shallow aquifer may be disregarded because of deficiency of pyrite in the shallow sediments, concomitant with depleted dissolved oxygen and very low levels of redox potentials of the As-polluted groundwater. The effect of wastewater from the general industrial area through a covered sewer stream was also considered as a possible source. Even though occurrence patterns of phenol and volatile organic hydrocarbons were very similar to those of the polluted shallow groundwater, As was not detected in the wastewater. One of the most plausible sources of the arsenic pollution was believed to be the reductive dissolution of Fe hydroxide. The As-polluted shallow groundwater had also very high levels of pH, HCO₃, COD and very low levels of DO and NO₃, which support the possibility of As pollution by the reductive dissolution. Consequently, the shallow groundwater in and around the NGMS has been polluted with various contaminants including As, phenol, chlorinated solvents, and petroleum hydrocarbons through multiple sources of contamination, such as natural reductive dissolution, dyeing wastewater, industrial wastewater, and municipal sewage.     

Environmental impact and geochemical behavior of soil contaminants from an industrial waste landfill in Southern Brazil

Industrial waste landfills produce great impacts on soil and groundwater. There are many industrial waste landfills in Vale dos Sinos, Southern Brazil, which were inadequately planned and maintained since the industry started in the first half of the twentieth century. The largest industrial landfill in the Valley, which causes the most severe impacts on soil and groundwater, is the subject of this paper, which studies the environmental impacts and behavior of contaminants in soil. The landfill was carefully mapped on a scale of 1:1,000; 88 samples were collected from soil probes; the leachate of three samples was comprehensively analyzed; and soils mineralogy and chemistry were studied. Few studies have been made on this landfill. This study shows widespread contamination of soil in the surrounding areas of the landfill. Chromium, chloride and ammonium have the highest contamination levels, reflecting their high contents in landfill leachate. Contamination by petroleum hydrocarbons, cyanide and mercury is registered in more than 65% of soil samples with low concentrations. Lead, copper and barium show low contamination restricted to a few soil samples. Soil contamination occurs mainly in the unsaturated zone of the aquifer at the convergence points of stormwater, showing that the preferential transport of contaminants occurs on surface flow followed by soil infiltration. The results of leaching tests indicate high metal sorption capacity of soil. The remediation of contaminated soil must contain at least the following actions: sealing the top of the landfill, installation of geochemical barriers, removal of the liquid waste basins without sealing the base and collection and treatment of the rainwater drainage.     

苯、甲苯对粒状铁去除四氯乙烯影响的柱实验研究

挥发性氯代烃和石油烃类污染是地下水中最常见的混合污染类型,而且这两类污染物毒性极强,对人类危害非常严重。文中选取具有代表性的四氯乙烯、苯和甲苯为研究对象,采用柱实验的方法研究苯和甲苯在粒状铁反应系统中吸附平衡后,对粒状铁去除四氯乙烯的机理及反应动力学的影响。在实验装置运行的过程中,苯、甲苯和四氯乙烯的浓度始终控制在2mg/L左右的水平。实验结果表明:苯或甲苯的存在对被还原的产物组成没有影响,主要氯代中间产物均为TCE、1,1-DCE、cis-1,2-DCE和VC,但组成比例略有不同。苯和甲苯的存在对去除速率有影响,即苯对四氯乙烯的去除有促进作用,去除速率平均提高13.5%;而甲苯则抑制四氯乙烯的去除,去除速率平均降低13.8%。对比控制柱,苯和甲苯存在时对出水水化学变化的影响没有明显差异。