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.     

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。     

牡蛎壳改性及联合释氧复合材料修复地下水氨氮污染实验研究

为研究以牡蛎壳-释氧复合材料为填料的渗透反应格栅去除地下水氨氮污染的效果及其经济实用性,开展了相关室内实验:采用高温加热方式对牡蛎壳进行改性,通过测定牡蛎壳改性后的比表面积判定其吸附效果;以过氧化钙为释氧化合物,将其与水泥、石英砂/牡蛎壳粒、钙基膨润土以一定比例混合制成粒径约1.8 cm球型释氧材料,采用静态实验研究不同原料配比的释氧材料的释氧性能;最后研究了两种不同粒径牡蛎壳粒-释氧复合材料修复地下水氨氮的效果及不同供氧方式下不同吸附材料修复地下水氨氮的效果及其经济实用性。结果表明:对牡蛎壳粒进行高温改性,牡蛎壳粒高温条件下会产生团聚现象,比表面积随煅烧温度升高呈下降趋势,高温改性方式并不能有效改善牡蛎壳粒吸附性能;实验中制作的释氧材料在95天的实验期间,各实验柱的溶解氧量可以保持在18 mg/L左右,且在嗜碱菌作用下pH值得以有效降低,所制作的释氧材料可为硝化细菌长期在溶解氧低的地下水环境中生长提供氧气;以牡蛎壳-释氧复合材料为填料的渗透反应格栅通过耐碱硝化细菌的硝化作用可以将氨氮浓度从50 mg/L降至约35 mg/L,不同粒径牡蛎壳粒修复效果差异不明显。使用牡蛎壳-释氧复合材料渗透反应格栅长期修复地下水氨氮,不仅可以达到活性炭及沸石作为骨架的修复效果,而且更加具有经济实用性。     

Occurrence and consequences of acid sulphate soils and methods of site remediation

The oxidation of sulphides in acid sulphate soils (ASS) causes the acidification of many Australian coastal river systems. The acidity negatively impacts upon coastal ecosystems, aquaculture, agriculture and concrete and steel infrastructure. In the low-lying floodplains, relatively deep surface drains fitted with one-way floodgates lower the watertable, thereby exposing the sulphidic minerals to oxidation. On the Broughton Creek floodplain in SE Australia, four distinct remediation strategies have been developed to tackle the issue of acidification by ASS: (i) simple V-notch weirs that raise the level of the watertable surrounding the drains thereby submerging the pyrite and preventing the further formation of acidity; (ii) modified two-way floodgates that allow the inflow of tidal water into the drains, thereby buffering the acidity within the drain before it enters the river and raising the level of the watertable surrounding the drain; (iii) lateral impermeable lime barriers that both prevent oxidation of pyrite by stopping the downward movement of oxygen into the soil and neutralise the acidity in the groundwater; and (iv) permeable reactive barriers (PRB) that passively intercept the groundwater flow and neutralise the acidity. Each remediation strategy has a distinct role to suit the different terrain and groundwater conditions.     

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.     

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.     

An assessment of the utilization of waste resources for the immobilization of Pb and Cu in the soil from a Korean military shooting range

Military shooting range soils contaminated by heavy metals have been subjected to remediation efforts to alleviate the detrimental effects of exposure on humans and the surrounding environment. Waste materials can be used as cost-effective soil amendments to immobilize heavy metals in contaminated soils. In this study, naturally occurring lime-based waste materials including egg shells, oyster shells, and mussel shells were assessed for their effectiveness toward heavy metal immobilization in military shooting range soil in Korea. Soil was treated in batch leaching experiments with 0, 2.5, 5, 10, and 15% of each lime-based waste material. The results showed that the lime-based waste materials effectively reduced water-soluble Pb at an application rate of 2.5% by weight of the soil. Increase in soil pH from 6.6 to 8.0 was considered to be the main chemistry of Pb immobilization, which was supported by the formation of insoluble Pb species at high pH values as confirmed by the visual MINTEQ thermodynamic model. In contrary, water-soluble Cu was increased in the lime-based waste material-treated soils when compared to the untreated soil. This was likely attributed to the formation of soluble Cu?CDOC (dissolved organic carbon) complexes as all lime-based waste materials applied increased DOC contents in the soil. Therefore, care must be taken in selecting the appropriate amendment for immobilizing metals in shooting range soils.     

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.     

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.     

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。     

Reactive transport modelling of Cr(VI) treatment by cast iron under fast flow conditions

The Cr(VI) reduction behaviour of five different types of grey cast iron shavings meant for construction of a permeable reactive barrier (PRB) in Thun, Switzerland, was investigated by performing batch and column experiments. Closed system batch experiments clearly demonstrated that the largest shavings also containing the largest spherical C inclusions, were best qualified for the PRB due to their fast Cr(VI) reduction rate. However, the column experiment performed with this type of material revealed that a complete and long term Cr(VI) treatment by the planned PRB was questionable due to the site-specific high groundwater flow velocities and the almost O₂ and CaCO₃ saturated aquifer conditions. The experimentally observed Cr(VI) breakthrough is explained as a result of a decline of reactivity provoked by a strong passivation by observed Fe hydroxides (FeOOH-polymorphs) and carbonates (calcite and aragonite).The column experiment was simulated using the reactive transport modelling code CrunchFlow. Iron cycling and intra-aqueous reactions were incorporated into a previously described reaction network in order to model the strong decline in reactivity of grey cast iron. All key parameters like aqueous species concentrations and mineralogical evolution of the column were successfully modelled. The modelling results confirmed that the observed Cr(VI) breakthrough was caused by surface passivation of the Fe shavings. Complete oxidation of the initially present mass of shavings is not predicted to occur during the expected PRB lifetime of several decades. The model seems to be robust, and it is expected that an application of the calibrated model in 2D to field sites will allow a quantitative evaluation for the performance of planned PRB’s in such environments.     

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。     

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.     

地下水中氯代烃的格栅水处理技术

挥发性氯代烃是地下水中检出率较高的有机污染物 ,同时也是饮用水氯气消毒的副产物 ,而它对人体的危害也已经得到了USEPA等机构的认同。文中主要从格栅材料、降解机理、影响还原性脱氯效率的因素、实际工程中应注意的问题以及发展方向等方面 ,对地下水中挥发性氯代烃的处理技术进行了阐述 ,介绍了格栅处理地下水中挥发性氯代烃的最新进展和实际意义 ,提出了格栅系统的实际应用潜力和存在的问题 ,特别是双金属系统的催化机理和催化剂失活问题 ,给国内这方面的研究者提供思路。     

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.     

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 of TCE-contaminated groundwater using zero valent iron and direct current: experimental results and electron competition model

The objectives of this study are to design an optimal electro-enhanced permeable reactive barrier (E2PRB) system for the remediation of trichloroethylene (TCE)-contaminated water using zero valent iron (ZVI) and direct current (DC) and to investigate the mechanisms responsible for TCE degradation in different ZVI-DC configurations. A series of column experiments was conducted to evaluate the effect of different arrangements of electrodes and ZVI barriers in the column on the TCE removal capacity (RC). In twelve different combinations of ZVI and/or DC application in the test columns, the rate of reductive dechlorination of TCE was improved up to six times with simultaneous application of ZVI and DC compared to that using ZVI only. The most effective arrangement of electrode and ZVI for TCE removal was the column set with ZVI and a cathode installed at the down gradient. Based on the electrokinetic study for the column systems with only DC input, single acid front movement could explain different RCs. An enhanced dechlorination rate of TCE using E2PRB systems, compared to a conventional PRB system, was observed, and is considered to be attributed to more electron sources: (1) external DC, (2) electrolysis of water, (3) oxidation of ZVI, (4) oxidation of dissolved Fe²⁺, (5) oxidation of molecular hydrogen at the cathode, and (6) oxidation of Fe²⁺ in mineral precipitates. Each of these electron sources was evaluated for their potential influencing the TCE RC through the electron competition model and energy consumption. A strong correlation between the quantity of electrons generated, RC, and the energy-effectiveness was found.     

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.      

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。     

Remediation of ground water containing chlorinated and brominated hydrocarbons, benzene and chromate by sequential treatment using ZVI and GAC

A laboratory experiment with two sequenced columns was performed as a preliminary study for the installation of a permeable reactive barrier (PRB) at a site where a mixed ground water contamination exists. The first column contained granular zero valent iron (ZVI), the second column was filled with granular activated carbon (GAC). Trichloromethane (TCM, 930 μg/l) and chlorobenzene (MCB, 260 μg/l) were added to the ground water from the site as the main contaminants. Smaller amounts (<60 μg/l) of benzene, 1,2-dichloroethane, 1,1,2-trichloroethane (1,1,2-TCA), 1,1-dichloroethene (1,1-DCE), trichloroethene (TCE), tetrachloroethene (PCE), 1,2-dichloropropane (1,2-DCP), bromodichloromethane (BDCM), dibromochloromethane (DBCM), tribromomethane (TBM), vinyl chloride and chromate were also added to the water to simulate the complex contamination pattern at the site of interest. PCE, TCE, 1,1-DCE, DBCM, BDCM, TBM, MCB and chromate were remediated in contact with ZVI, while the remaining contaminants showed incomplete degradation. A fraction of 8–16.5% TCM was converted to dichloromethane (DCM). Remaining contaminant concentrations were efficiently sorbed by the GAC until breakthrough of DCM was observed after 1,230 exchanged pore volumes in the GAC. The results show that the complex mixture of contaminants can be remediated by a sequenced PRB consisting of ZVI and GAC and that DCM sorption capacity is the critical parameter for the dimensions of the GAC reactor.