The application of in situ permeable reactive (zero-valent iron) barrier technology for the remediation of chromate-contaminated groundwater: a field test

A small-scale field test was initiated in September 1994 to evaluate the in situ remediation of groundwater contaminated with chromate using a permeable reactive barrier composed of a mixture of zero-valent Fe, sand and aquifer sediment. The site used was an old chrome-plating facility located on a U.S. Coast Guard air base near Elizabeth City, North Carolina. Dissolved chromate concentrations were reduced to less than 0.01 mg/L via reduction from Cr(VI) to Cr(III) as a result of the corrosion of the Fe. As the Fe corrodes, pH increases, oxidation-reduction potential declines, dissolved oxygen is consumed, and Fe(II) is generated. Mineral phases formed as a result of the Fe corrosion include ferrous sulfides and various Fe oxides, hydroxides, and oxyhydroxides.     

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.     

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。     

利用动电模型分析黏土渗流的耦合动力学性状

从水头?诱导电位耦合驱动的角度,探讨分析黏土?水溶液体系的流体动力学性状。为此,借助动电输运原理,耦合Poisson-Boltzmann、Nernst-Planck、Navier-Stokes方程,建立了“广义力”驱动“广义流”的耦合关系。模型从黏土代表性单元体入手,计算确定各项耦合系数,用以定量考察离子迁移、流体运动的耦合性状。计算表明：采用Debye-Huckel近似计算黏土双电层电位将引起显著的误差;诱导电位产生的原因在于维持体系的电中性,其梯度大小正比于正负离子间因水头迁移性的差异而产生的潜在分离程度;诱导电位作用于离子迁移的方式在于阻滞正离子迁移,助推负离子迁移,而作用于流体运动的方式在于引起反向电渗,进而削弱水头驱动下的正向渗流;高表面带电密度的黏土矿物（如蒙脱土）处于低孔隙率的状态时,诱导电位对于渗流的削弱程度有可能异常显著。因此,建议相应的水头渗透系数的测定需要充分考虑诱导电位的影响,否则将导致较为显著的误差。     

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.     

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。     

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.     

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).     

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。     

Atmospheric pressure dielectric barrier discharge for the remediation of soil contaminated by organic pollutants

The remediation of soil, contaminated by organic pollutants, in a cylinder-to-plane dielectric barrier discharge reactor at atmospheric air pressure was reported. Two model organic pollutants were selected; a solid pollutant (2,6-dichloropyridine) and a liquid pollutant (n-dodecane). The effects of the contaminant’s initial concentration and state, the energy consumption, and the soil type on the pollutant removal efficiency were investigated. To that scope, various contaminated samples of both quartz sand and loamy sandy soil were treated by plasma for various treatment times and initial 2,6-dichloropyridine/n-dodecane concentrations. The results revealed that (1) the removal efficiency of 2,6-dichloropyridine was higher compared to that of n-dodecane at a given plasma treatment time and (2) the removal efficiency increased with the energy density increasing, but decreased as the soil heterogeneity, organic matter and pollutant concentration were enhanced. The main removal mechanism proposed is the evaporation of pollutant molecules coupled with their oxidation by plasma species in the gas and solid/liquid phase.     

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.     

Remediation with surfactant foam of PCP-contaminated soil

An investigation was made into evaluating the capability of surfactants in the form of foam for removing the contaminant pentachlorophenol (PCP), a highly toxic, wood preservative, from soil. Several surfactants were investigated for their ability to make foam. Two of them, Triton X-100 and JBR425 (a rhamnolipid biosurfactant), generated foam with higher quality (99%) and higher stability than other surfactants. Triton X-100 and JBR425 were then used to investigate the removal efficiency in soils contaminated with pentachlorophenol (PCP). Triton X-100 showed better results in terms of final removal efficiency. Triton X-100 (1%) removed 85% and 84% of PCP from fine sand soil and sandy-silt, respectively, contaminated with 1000 mg/kg PCP. These values were 60% and 61% for JBR425 (1%). Of this, 66% and 57% of the PCP was removed by volatilization by Triton X-100 and 36% and 44% by JBR425. Further experiments with Triton X-100 indicated that 1% Triton X-100 removed more than 0.5% and that PCP removal was approximately the same for 1% Triton X-100 for a higher contaminant level (3000 mg/kg) but more pore volumes of foam were required for fine sand (23 pore volumes compared to 12). For the sandy-silt soil, PCP removal was higher for the higher contaminant level, 84% compared to 76%. More pore volumes were required (35 compared to 21). Comparison of liquid and foam injection of 1% Triton X-100 indicated that the foam removed more than twice as much PCP in all cases than the liquid surfactant solution. The results of this study on a sandy and sandy-silt media, thus, found that the foam can be used as a fluid to enhance soil remediation under low pressures compared to other fluids such as liquid surfactant solutions.     

淋滤条件下GGBS-MgO固化铅污染黏土强度与溶出特性研究

以粒化高炉矿渣粉-氧化镁（GGBS-MgO）固化铅污染黏土为研究对象,通过半动态淋滤试验,对GGBS-MgO在酸雨作用下的强度特性及溶出特性进行研究。通过对GGBS-MgO固化铅污染黏土半动态淋滤后pH值、针刺深度、无侧限抗压强度及浸出液中[Pb]、[Ca]、[Mg]元素浓度的测试,分析淋滤液初始pH值、掺量以及含铅不含铅对GGBS-MgO固化土强度特性的影响,讨论了初始淋滤液pH值、固化剂掺量对GGBS-MgO固化铅污染土累积铅、钙、镁溶出质量以及铅有效扩散系数的影响规律。结果表明,半动态淋滤试验使试样无侧限抗压强度qu较标准养护39 d试样降低了2%～53%,且淋滤液初始pH=2对试样qu影响最大;在相同掺量、相同淋滤液初始pH值时,GGBS-MgO固化未污染土半动态淋滤后qu较水泥固化未污染土qu提高了12%～43%;且当固化剂掺量为18%时,固化铅污染土强度特性较水泥有明显优势,约为水泥固化铅污染土强度的1.3～1.8倍;且相同配比时,淋滤液初始pH=2表层的pH值约为pH=3、4、5、7的1/2;随着淋滤液初始pH值、半动态淋滤后qu及内部pH值的增加,针刺深度减小;针贯入阻力与qu存在幂指数关系。此外,累积铅、钙、镁溶出质量随着初始淋滤液pH值、固化剂掺量的增加而减少,在初始淋滤液pH=2时,Ai,Pb、Ai,Ca、Ai,Mg分别约为pH=3、4、5和7的29～222倍、1.7～4.4倍和12.0～80.3倍;固化剂掺量为12%时的累积溶出质量约是18%掺量时的1.1～2.0倍;铅有效扩散系数De随着初始淋滤液pH值的增加而降低,初始淋滤液pH=2时的De比pH=3～7的De高约3～5个数量级;且低于水泥固化铅污染土De,当初始淋滤液pH=7时,GGBS-MgO固化土De相比于水泥固化土低1～2个数量级。     

Remediation of saturated Shanghai sandy silt contaminated with p-xylene using air sparging

Air sparging is an effective technique for the remediation of soil and groundwater polluted by volatile organic compounds. In this paper, this technique was investigated by conducting air-sparging test in the laboratory on the Shanghai sandy silt that was artificially contaminated with p-xylene. A test tank was designed for this purpose. During the air-sparging process, aqueous p-xylene solutions were extracted from the observation holes, and their concentrations were quantified by the spectrophotometric detection method. The mechanism of mass transfer process of p-xylene in the vicinity of sparging well and the remediation of the contaminated groundwater by air sparging were explored. The results showed that the removal zone of the p-xylene was mainly located within a radius of about 20?cm around the air injection well, with 90?% p-xylene removed after 20-day air sparging. Within the initial 5-day sparging, the concentration of p-xylene decreased rapidly in the mass transfer zone. By contrast, in the area far from the injection well, the p-xylene concentration decreased evenly and slowly. Thus, the remediation of contaminated soil and groundwater by air sparging is space?Ctime dependent. For further analysis, the adsorption of silt was taken into account, and the distribution coefficient, K _d , was introduced to the modified Shackleford??s mass transfer model. The comparison between the simulated and measured results indicates that the modified model can satisfactorily describe the p-xylene mass transfer observed in this study.     

Phytoremediation of soil contaminated by heavy oil with plants colonized by mycorrhizal fungi

The purpose of this study was to investigate the effect of phytoremediation on soils contaminated with heavy crude oil using plants infected by mycorrhizal fungi. Five plant species, Vetiveria zizanioides, Bidens pilosa, Chloris barbata, Eleusine indica, and Imperata cylindrica, infected with the species of mycorrhizal fungi Glomus mosseae, were selected for this study. The degradation of total petroleum hydrocarbons in soils and several physiological parameters of plants such as shoot length and biomass were analyzed. Out of the 5 plant species tested, only V. zizanioides, B. pilosa, and E. indica could take up the G. mosseae. Out of these three, V. zizanioides showed the greatest growth (biomass) in soils with 100,000 mg kg^?1 total petroleum hydrocarbons. In addition, B. pilosa infected with G. mosseae was found to be able to increase degradation by 9 % under an initial total petroleum hydrocarbons concentration of 30,000 mg kg^?1 in soils after 64 days. We conclude that plants infected with mycorrhizal fungi can enhance the phytoremediation efficiency of soils contaminated with high concentrations of heavy oil.     

Characterization and constitutive modeling of red clay contaminated with ammonium carbonate

Conventionally, red clay is used for agricultural purposes in southern China. Fertilizers, especially urea, are commonly introduced into the red clay to improve the crop yields. However, due to the rapid urbanization in China, large areas of lands with red clays have been converted into sites for domestic and industrial constructions. Nevertheless, few researchers focused on the effect of urea on the strength and compressibility of red clay. In this research, the shear strength and compressibility of the red clay saturated by different concentrations of the (NH₄)₂CO₃ solution (urea's hydrolysates) were experimentally investigated using direct shear as well as oedometer tests, respectively. It was noticed that both the shear strength and stiffness of the red clay significantly decreased after exposure to the urea solution. In addition, the micromechanisms of the strength and compressibility of the red clay treated by the (NH₄)₂CO₃ were studied by the scanning electron microscope test and X-ray diffraction test. Based on the test results, a new model was developed to simulate the chemomechanical behavior of saturated clayey soil by modifying the Barcelona basic model (BBM) for unsaturated soils. The proposed model introduces four additional parameters, compared to the BBM, to account for the nonlinear shear strength behavior of the red clay. This model accounts for most of the complex features related to the strength and stiffness behavior of clayey soils. The parameter calibration procedures, by using the oedometer and direct shear test results, are also presented. To validate the proposed model, experimental results from the literature are considered in which illite clay samples were either mechanically or chemically or both mechanically and chemically loaded. Part of the experimental results is used to calibrate the model parameters and the other part along with the calibrated parameters is used to verify the proposed model. A comparison between experimental data and predicted results demonstrated that the proposed model is able to capture the main features related to the chemomechanical coupling behavior of saturated soils.     

连续渗透边界下非饱和土竖井地基固结解析解EI北大核心CSCD

基于非饱和土轴对称固结理论和等应变假设,引入连续渗透边界条件,采用边界条件齐次化、本征函数法,推导得到瞬时均布荷载下非饱和土竖井地基三维固结解析解。通过与双面完全渗透边界条件下已有解析解进行对比,验证了所得解析解的正确性。对所得解进行算例分析发现:通过设置合理上、下界面参数,所得解可用于模拟实际上、下边界透水透气任意分布的情况,弥补了目前无法考虑上、下边界渗透性介于渗透与不渗透之间或不对称分布的不足;在井径比及井深适当的前提下,当径、竖向渗透系数比大于2时,竖向渗流对于超孔隙压力消散的影响较小;当考虑竖向渗流时,上述影响随着上、下边界渗透性能的增强而愈加明显。     

Development of modified flyash as a permeable reactive barrier medium for a former manufactured gas plant site, Northern Ireland

A sequential biological permeable reactive barrier (PRB) was determined to be the best option for remediating groundwater that has become contaminated with a wide range of organic contaminants (i.e., benzene, toluene, ethylbenzene, xylene and polyaromatic hydrocarbons), heavy metals (i.e., lead and arsenic), and cyanide at a former manufactured gas plant after 150 years of operation in Portadown, Northern Ireland. The objective of this study was to develop a modified flyash that could be used in the initial cell within a sequential biological PRB to filter complex contaminated groundwater containing ammonium. Flyash modified with lime (CaOH) and alum was subjected to a series of batch tests which investigated the modified cation exchange capacity (CEC) and rate of removal of anions and cations from the solution. These tests showed that a high flyash composition medium (80%) could remove 8.65 mol of ammonium contaminant for every kilogram of medium. The modified CEC procedure ruled out the possibility of cation exchange as the major removal mechanism. The medium could also adsorb anions as well as cations (i.e., Pb and Cr), but not with the same capacity. The initial mechanism for Pb and Cr removal is probably precipitation. This is followed by sorption, which is possibly the only mechanism for the removal of dichromate anions. Scanning electron microscopic analysis revealed very small (<1 μm) cubic highly crystalline precipitates on the flyash, although this new crystalline zeolite growth did not occur rapidly enough to enable productive zeolite formation. Surface area measurements showed that biofilm growth on the medium could be a major factor in the comparative reduction of surface area between real and synthetic contaminant groundwaters. The modified flyash was found to be a highly sorptive granular material that did not inhibit microbiological activity, however, leaching tests revealed that the medium would fail as a long-term barrier material.     

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.