Long-term performance evaluation of zero-valent iron amended permeable reactive barriers for groundwater remediation – A mechanistic approach

Permeable reactive barriers (PRBs) are used for groundwater remediation at contaminated sites worldwide. This technology has been efficient at appropriate sites for treating organic and inorganic contaminants using zero-valent iron (ZVI) as a reductant and as a reactive material. Continued development of the technology over the years suggests that a robust understanding of PRB performance and the mechanisms involved is still lacking. Conflicting information in the scientific literature downplays the critical role of ZVI corrosion in the remediation of various organic and inorganic pollutants. Additionally, there is a lack of information on how different mechanisms act in tandem to affect ZVI-groundwater systems through time. In this review paper, we describe the underlying mechanisms of PRB performance and remove isolated misconceptions. We discuss the primary mechanisms of ZVI transformation and aging in PRBs and the role of iron corrosion products. We review numerous sites to reinforce our understanding of the interactions between groundwater contaminants and ZVI and the authigenic minerals that form within PRBs. Our findings show that ZVI corrosion products and mineral precipitates play critical roles in the long-term performance of PRBs by influencing the reactivity of ZVI. Pore occlusion by mineral precipitates occurs at the influent side of PRBs and is enhanced by dissolved oxygen and groundwater rich in dissolved solids and high alkalinity, which negatively impacts hydraulic conductivity, allowing contaminants to potentially bypass the treatment zone. Further development of site characterization tools and models is needed to support effective PRB designs for groundwater remediation.     

某Cr(Ⅵ)污染场地修复的PRB反应材料及结构设计研究

渗透反应格栅(permeable reactive barrier,PRB)在国外被广泛应用于场地尺度的地下水污染修复,因其无须外源动力、不占地面空间、运行成本低等优势在国内受到广泛关注。不同场地水文地质条件、污染物类型、污染羽分布具有差异性,前期场地调查、反应材料的筛选、反应墙尺寸结构的设计对于PRB的有效运行至关重要。本文以PRB修复河南某Cr(Ⅵ)污染场地为例,详细阐述场地调查、材料筛选、材料反应参数确定、PRB结构优化等方面的研究过程及成果,可为后续PRB修复技术的应用提供参考。研究结果表明:PRB修复技术适用于该场地,铸铁与活性炭混合材料为最佳修复材料;反应门长40 m(反应材料厚2 m,上下游分别为2 m厚砾石层),东西两侧隔水墙长为60 m的U型漏斗-门系统型PRB,可有效捕获并修复污染羽,工程成本远低于连续反应墙式PRB,为该场地修复最优PRB结构类型。     

一维流动条件下PCE链式降解中PRB厚度解析及影响

可渗透反应墙（Permeable Reactive Barrier,PRB）技术是原位地下水或者土壤修复中最受瞩目的技术之一,该技术设计和安装的首要关键问题就是反应墙的厚度计算.现有的反应墙设计方法大部分只考虑了单一污染物或者反应墙本身,很少考虑多种污染物的存在以及含水层水力性质的实际情况.聚焦于可渗透反应墙中的PCE（四氯乙烯）链式降解过程,基于可渗透反应墙-含水层的多域多组分污染物的体系建立了一维条件下的对流弥散方程,通过借鉴相关文献提出的转换算法得出方程解析解,并由此推导出适合多组分污染物体系的反应墙厚度公式,利用软件COMSOL建立了数值模型验证了其正确性.对比已有的Rabideau模型发现:计算反应墙厚度时不能完全忽略含水层的自然衰减反应,尤其当达标面远离反应墙出口处时;对于多种组分皆来源于同一种母源反应物的污染物,计算反应墙厚度时边界条件十分关键.本文模型的解析解可以为可渗透反应墙的设计和安装提供建设性的意见,还可以快速分析多组分污染物的分布和预测,为地下水的修复工程、风险评估、后期监测控制提供了计算的支撑.      

Optimization of a PRB structure with modified chitosan restoring Cr(VI)-contaminated groundwater

Hexavalent chromium is a soluble, mobile, and highly toxic metal ion in groundwater. Adsorption by permeable reactive barriers (PRBs) with special sorbent is a common method to remove hexavalent chromium. A series of experiments have been performed to remove hexavalent chromium in groundwater under PRB with modified chitosan. Therefore, in this paper, the authors first estimated adsorption characteristics of the modified chitosan in a column test, and then calibrated the PRB adsorption parameters in a sandbox test, and finally designed an optimal width, length, and depth of the PRB with the same reactive media in a three-dimensional aquifer. The results showed that the modified chitosan might be a potential adsorption medium. The design schemes can meet the water quality standard of 0.1 mg/L Cr(VI). Heterogeneity of dispersion is a crucial factor when designing the PRB. Therefore, the design of the PRB structures can be appropriate and serve as reference for groundwater remediation.     

Permeable Reactive Barrier for Groundwater Pollution Remediation: An Review

As an in situ, simple and passive technology, Permeable Reactive Barrier (PRB) is becoming widely used in groundwater remediation. Based on its definition and development process, the development of PRB can be divided into two stages: The traditional zero-valent iron PRB before 2000 and the PRB composed of novel mixed media after 2000. With the rapid worsening of groundwater pollution, the increasing application of PRB and the rapid development of materials science, the development of PRB technology in future will be mainly focused on the investigation of mixed and novel media, the design of mixed PRBs, the combination of PRB technology with other remediation technology, and the long term monitoring and management of PRB projects.     

不同介质材料组合可渗透反应墙渗透性能试验研究

渗透系数是可渗透反应墙(PRB)正常运行的关键参数之一,与PRB活性填充材料的选择密切相关。本试验采用常水头渗透系数测试法,首先选用斜发沸石、红辉沸石为作为PRB的活性介质材料,考察了沸石矿物的类型和粒径对PRB渗透系数的影响,试验结果显示,同一粒径的斜发沸石PRB和红辉沸石PRB渗透系数相差一个数量级;处于同一数量级渗透系数沸石PRB,斜发沸石的粒径大于红辉沸石的粒径。在此基础上,以膨润土作为掺和活性介质材料,讨论了渗透系数处于同一数量级沸石PRB,掺和比例对渗透系数的影响,结果表明,膨润土的掺和能导致沸石PRB渗透系数量级上的差异,与斜发沸石相比,红辉沸石更有利于实现沸石PRB系统渗透系数的可调性。     

Unraveling the partial failure of a permeable reactive barrier using a multi-tracer experiment and Cr isotope measurements

At a Cr(VI) contaminated site in Thun, Switzerland, a permeable reactive barrier (PRB) was installed in 2008. Downstream Cr(VI) concentrations did not indicate any sign of its successful operation more than 2 years after PRB installation. The cause for this potential PRB failure was investigated by performing Cr isotope measurements and a multi-tracer experiment. The combination of reactive (Cr isotopes) and non-reactive tracers allowed characterizing the groundwater flow regime in the vicinity of the PRB in detail. In particular, it could be confirmed that most of the Cr(VI) load is currently bypassing the barrier, whereas only a minor Cr(VI) load is flowing through the PRB. Fitting of observed breakthrough curves using a conventional advection dispersion model resulted in average linear flow velocities of 13–15 m/day for the bypassing Cr(VI) load and 4–5 m/day for the Cr(VI) flowing through the barrier. Using a Rayleigh fractionation model a Cr(VI) reduction efficiency of 77–98% was estimated for the Cr(VI) load that is flowing through the barrier. In contrast, a value of 0–23% was estimated for the current overall PRB reduction efficiency. It is concluded that the PRB bypass and the low overall Cr(VI) reduction efficiency are caused by a limited PRB permeability inherited from skin effects that occurred during PRB emplacement.     

中试尺度下可渗透反应墙位置优化模拟——以铬污染地下水场地为例

可渗透反应墙（PRB）是一种高效的地下水污染原位修复技术。不同水文地质条件下,污染场地墙体位置布设合理性影响其修复效果,而利用地下水数值模拟可实现墙体位置优化。文章以某Cr6+污染地下水场地为例,基于Visual Modflow建立了研究区平面二维稳定流数值模型,并通过模型检验。根据墙体的设计尺寸（长20 m×宽2 m×深12 m）及填充材料的渗透系数（80 m/d）,利用所建模型分别计算了4种布设方案（墙体尺寸大小和填充材料渗透系数相同,布设位置不同）下墙体的捕获区宽度、粒子滞留时间和通过墙体的Cr6+通量。结果表明:4种布设方案模拟的滞留时间和捕获区宽度取值差异性不大,变异系数小于2%;Cr6+通量差别较大,变异系数高达76.32%,主要由地下水中Cr6+浓度空间分布不均引起。对比分析4种方案的各评价指标,方案2求得的捕获区宽度为21.9 m,粒子滞留时间为4.1 d,Cr6+去除量可达127.7 mg/d,可作为最佳布设方案。本研究建立的地下水流数值模型符合场地实际情况,可有效评估PRB截获污染羽的范围和去除目标污染物的能力,为铬渣类污染场地PRB原位修复工程设计与实施提供技术支撑和参考依据。     

Selection of permeable reactive barrier materials for treating acidic groundwater in acid sulphate soil terrains based on laboratory column tests

The Shoalhaven region of NSW experiences environmental acidification due to acid sulphate soils (ASS). In order to trial an environmental engineering solution to groundwater remediation involving a permeable reactive barrier (PRB), comprehensive site characterisation and laboratory-based batch and column tests of reactive materials were conducted. The PRB is designed to perform in situ remediation of the acidic groundwater (pH 3) that is generated in ASS. Twenty-five alkaline reactive materials have been tested for suitability for the barrier, with an emphasis on waste materials, including waste concrete, limestone, calcite-bearing zeolitic breccia, blast furnace slag and oyster shells. Following three phases of batch tests, two waste materials (waste concrete and oyster shells) were chosen for column tests that simulate flow conditions through the barrier and using acidic water from the field site (pH 3). Both waste materials successfully treated with the acidic water, for example, after 300 pore volumes, the oyster shells still neutralised the water (pH 7).     

Using dissolved gas analysis to investigate the performance of an organic carbon permeable reactive barrier for the treatment of mine drainage

The strongly reducing nature of permeable reactive barrier (PRB) treatment materials can lead to gas production, potentially resulting in the formation of gas bubbles and ebullition. Degassing in organic C based PRB systems due to the production of gases (primarily CO₂ and CH₄) is investigated using the depletion of naturally occurring non-reactive gases Ar and N₂, to identify, confirm, and quantify chemical and physical processes. Sampling and analysis of dissolved gases were performed at the Nickel Rim Mine Organic Carbon PRB, which was designed for the treatment of groundwater contaminated by low quality mine drainage characterized by slightly acidic pH, and elevated Fe(II) and SO₄ concentrations. A simple 4-gas degassing model was used to analyze the dissolved gas data, and the results indicate that SO₄ reduction is by far the dominant process of organic C consumption within the barrier. The data provided additional information to delineate rates of microbially mediated SO₄ reduction and confirm the presence of slow and fast flow zones within the barrier. Degassing was incorporated into multicomponent reactive transport simulations for the barrier and the simulations were successful in reproducing observed dissolved gas trends.     

Feasibility of using fly ash,lime, and bentonite to neutralize acidity of pore fluids

Acidic groundwater resulting from the poorly planned use of acid sulfate soils has become a major environmental issue in coastal Australia over the last several years. Use of permeable reactive barriers (PRBs) designed to generate alkalinity by promoting sulfate reduction has recently become popular as an alternative solution to this problem. However, recent studies have also revealed that the long-term performance of such PRBs can be significantly undermined by chemical precipitation and clogging of pore space, which would decrease the buffer capacity and hydraulic conductivity of the reactive material. This study seeks to explore the feasibility of using bentonite in addition to lime and fly ash to form mixtures with a high buffer capacity and permeability that would enable groundwater flow through PRBs over a substantial period of time. A series of laboratory experiments, including buffer capacity and leaching tests, were performed on different mixtures of fly ash with lime and bentonite using acidic fluids of low pH. It was found that the ability of such mixtures to neutralize acidic fluids was mostly controlled by the content of lime. Laboratory data also showed that an addition of bentonite to lime—fly ash mixtures could decrease the buffer capacity of soil. Compaction tests indicated that the presence of bentonite would increase the dry density of mixtures at the optimum moisture content. A series of hydraulic conductivity tests were carried out to study changes in the coefficient of permeability of lime—fly ash mixtures with different contents of bentonite permeated with acidic liquids. The obtained results revealed that the coefficient of permeability of the specimens tended to increase over a period of time, likely due to the changes in the diffuse double layer of bentonite particles.     

可渗透反应墙处理垃圾渗滤液的实验研究

文章以垃圾渗滤液为研究对象,分别用铁粉、改性膨润土、活性炭及其混合物为反应介质,设计4种不同介质配比的PRB反应器进行实验研究。结果表明,PRB对垃圾渗滤液有较好的处理效果,其中,以还原铁粉、改性膨润土为介质的反应器,对氨氮的去除效率最大为97.58%,以还原铁粉、活性炭为介质的反应器对COD的去除效率为84.87%,对总磷的去除效率最大为80%。     

铁还原地下水环境中微生物降解苯和甲苯的碳源 专一性分析

文中研究在粒状铁化学还原三氯乙烯渗透反应格栅和生物降解苯和甲苯渗透反应格栅的联合格栅技术中,下游生物降解格栅中铁还原环境下微生物对苯和甲苯的生物降解。通过模拟粒状铁渗透反应格栅下游铁还原环境,主要研究微生物以苯、甲苯作为碳源时,对碳源的专一性。通过批实验发现,对于分别用苯和甲苯培养驯化的微生物,互换碳源后,微生物对2 000.00μg/L苯和甲苯的生物降解半衰期分别由之前的1.0和1.5 d减少到0.7和1.0 d,互换碳源后苯和甲苯的去除率分别增加38%和32%。在粒状铁渗透反应格栅下游生物降解渗透反应格栅中,微生物在铁还原环境下以苯、甲苯作为碳源时对碳源没有专一性,苯和甲苯可以同时被生物降解去除。     

Evaluation of mixtures of peat,zero-valent iron and alkalinity amendments for treatment of acid rock drainage

Reactive mixtures to be used in a permeable reactive barrier (PRB) for the treatment of low quality groundwater derived from a mine waste rock storage site were evaluated. Low pH drainage water from the site contained high concentrations of sulfate and dissolved metals, including Al, Co, Ni, and Zn. Column experiments were conducted to evaluate whether mixtures containing either peat moss (as an organic carbon source) or a mixture of peat moss and granular zero-valent iron (ZVI) filings, in addition to small amounts of lime and/or limestone, were suitable treatment materials for removing these metals from the water. The experimental results showed that the mixtures promote bacterially-mediated sulfate reduction and metal removal by precipitation of metal sulfides, metal carbonate/hydroxide precipitation, and adsorption under relatively high pH conditions (pH of 7–8). Both reactive mixtures removed influent dissolved metals to near or below the limit of detection in the effluent throughout the experiment; however, influent-level concentrations of the metals of interest gradually moved through the column containing peat alone, as the pH neutralizing ability in the mixture was consumed. In contrast, the column containing both peat and ZVI showed very little breakthrough of the influent metals, suggesting that the longevity of the mixture including ZVI will be much longer than the mixture containing peat alone. The results show that both reactive mixtures should be effective in a PRB installation as long as neutral pH conditions and microbial activity are maintained. The cost to performance ratio of the two reactive mixtures will be a key factor in determining which mixture is best suited for a particular site.     

混合PRB介质处理渗滤液污染地下水的可行性研究

反应介质的选择是可渗透反应墙(PRB)系统原位处理污染地下水的一个关键问题。本实验采用两种混合介质A(陶粒与活性炭的混合物)和B(沸石与活性炭的混合物),对修复被渗滤液污染的地下水的可行性进行了研究。结果表明,混合介质A和B对CODCr的平均去除率分别达到了71.8%和63.4%;对NH4 的平均去除率分别为13.5%和58.7%;对重金属的去除,反应介质B则优于A。因此,PRB反应介质的选择要根据污染物的性质而定。     

Coupled hydro-geochemical modelling of a permeable reactive barrier for treating acidic groundwater

This study focuses on coupling geochemistry with geo-hydraulics to enable time-dependent modelling of the remediation of acidic groundwater using an alkaline permeable reactive barrier (PRB). Chemical clogging due to secondary mineral precipitates reduces the porosity and hydraulic conductivity of the reactive medium. The governing equations are incorporated into commercial numerical codes, MODFLOW and RT3D. An original algorithm was developed for RT3D to simulate geochemical reactions occurring in the PRB. The results and the model predictions are in agreement, confirming that the hydraulic conductivity reduction due to mineral precipitation occurs at the start of permeation and continues until halfway through the testing phase.     

First results of operating and monitoring an innovative design of a permeable reactive barrier for the remediation of chromate contaminated groundwater

An innovative setup of a permeable reactive barrier (PRB) was installed in Willisau, Switzerland to remediate chromate contaminated groundwater. Instead of a conventional continuous barrier, this PRB consists of cylinders installed in rows: a single row for lower expected Cr^VI-concentrations and an offset double row for higher expected Cr^VI-concentrations. The cylinders are filled with reactive grey cast-Fe shavings mixed with gravel to prevent extensive precipitation of secondary phases in the pore space. The treatment of the contaminants takes place both within the cylinders and in the dissolved Fe^II plume generated downstream of the barrier. Monitoring of the contamination situation over a period of 3 a provided evidence of the mobilization, transport and behavior of the contaminants in the aquifer. Groundwater and reactive material were sampled upstream, within and downstream of the barrier by a Multi-Port Sampling System (MPSS) that revealed the geochemical processes as a function of time and space. Comprehensive chemical analyses included sensitive parameters such as Cr^VI, Fe^II/Fe^III, redox potential, dissolved O₂ and pH. Several campaigns using multiple optical tracers revealed a rather complex hydrological regime at different scales, thereby complicating the barrier performance.     

与铁相关的几种渗透反应格栅材料性能的比较

挥发性氯代有机化合物为地下水和饮用水中最常见的挥发性有机污染之一。文中对日益引人注意的渗透反应格栅(PRB:permeable reactive barrier)材料进行了研究。主要在实验室条件下,利用中国现有的实用性材料———铸铁的铁屑、实验室合成双金属和纳米双金属作为反应介质,对反应的脱氯效果和机理、还原性脱氯的反应动力学和影响因素进行初步的研究,以寻求一种可以大量得到的廉价而高效的材料,研究它对氯代烃的降解效率。在研究中选择最有代表性的CT和PCE作为目标污染物,讨论粒状铁、双金属以及纳米双金属对氯代有机物的降解速率,确定气相色谱法测定水溶液中的氯代有机物浓度的最佳实验条件,比较3 类反应介质的特点和应用范围。     

可渗透反应墙对重金属离子Pb~(2+)、Cd~(2+)吸附效果的试验研究

以受尾矿库渗滤液重金属离子Pb2+、Cd2+污染的地下水为研究对象,用天然矿物材料红辉沸石与膨润土作为反应渗透墙(PRB)的活性介质填充材料,试验结果表明,膨润土∶红辉沸石=1∶7,PRB渗透系数处于10-4cm/s数量级且随时间下降最为缓慢;PRB对单一组分Pb2+和单一组分Cd2+去除率分别达99.95%和99.995%;但在双组分PRB体系中,重金属离子Pb2+的存在显著地抑制了PRB对Cd2+的吸附作用,优先选择性吸附顺序是Pb2+Cd2+。     

Geochemistry analysis and evolution of a bolson aquifer,basin and range province in the southwestern united states

This paper expands significantly on the major-ion geochemical characterization, evolution, and differentiation of groundwater in the Presidio-Redford Bolson (PRB) Aquifer of Texas as presented in Chowdhury et al. (2008). For 19 groundwater samples from the PRB Aquifer, the author calculated major cation–anion balance errors, equilibrium carbon dioxide partial pressure values and saturation indices for selected minerals. Comparison of major-ion analyses for groundwater from basin margin wells with those for basin center wells is documented and illustrated with ion-concentration maps and Piper and Stiff diagrams and reveals significant increases in concentrations of chloride, sulfate and sodium coupled with notable decrease of calcium in bolson-center well samples. These geochemical changes suggest dissolution of aquifer minerals and cation exchange as groundwater migrates downgradient to the bolson center. The US Geological Survey (USGS) computer code, NETPATH, was used to interpret probable net geochemical mass-balance reactions that potentially have occurred within the PRB Aquifer along groundwater flowpaths from bolson margin to bolson center. For all four upgradient–downgradient well pairs studied, at least three NETPATH models contain cation exchange values; calcium is being exchanged for sodium. The Rio Grande Alluvium Aquifer and Rio Grande River are notably minor sources of recharge to the PRB Aquifer, based on Chowdhury et al. (2008) and geochemical evaluations of this study.