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。     

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40m(反应材料厚2m,上下游分别为2m厚砾石层),东西两侧隔水墙长为60m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。     

青海省海北化工厂Cr~(6+)污染调查评价与治理

海北化工厂已停产15年之久,但Cr6+污染依旧十分严重.调查得知,海北化工厂原生产废液排放及堆存废渣经降水淋滤作用下渗,是造成该区包气带和地下水Cr6+污染的主要原因.采用地下水质量法和污染指数法评价分析该区地下水Cr6+污染范围和污染影响程度.评价结果显示:Cr6+重度污染区面积0.75 km2,厂区包气带Cr6+平均含量67.67×10-6,平均超标指数1691.75,地下水中Cr6+浓度超过Ⅴ类水标准.在分析厂区周边水文地质条件的基础上,提出清除场地废渣废料并置换被污染的包气带、采用抽水法治理被污染的地下水的综合方案.     

青海海晏海北化工厂地下水Cr(Ⅵ)污染机理及治理方案

为研究青海省海晏县海北化工厂地下水Cr(Ⅵ)污染治理方案,在深入分析青海省海北化工厂一带环境水文地质条件、历年地下水及地表水环境Cr(Ⅵ)监测资料、地下水Cr(Ⅵ)点状污染源现状规模、污染羽空间展布特征以及地下水污染途径等的基础上,分析了海北化工厂地下水Cr(Ⅵ)污染地下水污染机理。基于此,从保护水环境的角度,经多方案比选,推荐可渗透反应墙(PRB)技术为修复治理海北化工厂Cr(Ⅵ)污染地下水的最佳方案。     

石油污染场地浅层地下水MNA原位修复潜能及微生物降解效益评估

监测式自然衰减（MNA）能够高效低耗地原位修复石油污染地下水的场地,微生物对污染物的降解对MNA过程起到了重要作用。在分析东北石油污染场地地下水中总石油烃（TPH）、电子受体的质量浓度分布和变化规律基础上,划分了微生物功能区。采用溶质通量计算法,对MNA原位修复的潜能及其微生物降解效果进行了评估。结果显示,场地微生物降解正在发生,利用的电子受体不同,划分为Mn、Fe和SO^2-₄还原区。污染通量模型计算显示：上游地区微生物降解强度不断增强,下游地区微生物降解强度不断降低。监测期内石油烃总量降低了394 kg,微生物降解为自然衰减过程中的主要作用,其贡献率为64%~93%,每个通量断面内微生物降解率为0.18~0.73 kg/d。由此可以证明,MNA可以有效地修复地下水中的石油污染。     

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+。     

邢台市岩溶水污染现状与演化趋势预测

由于地表水的污染和固体废物的乱堆放,导致邢台市岩溶水多处出现污染现象,且污染范围不断扩大,严重威胁下游水源地的供水安全。本文依据大量水质监测数据,评价了岩溶水的污染现状,采用数值方法预测了污染源继续存在和污染源得到治理两种情况下地下水污染的演化趋势,并分析了其对水源地的影响。预测结果表明:污染源存在时,地下水污染物Cr6+超标浓度等值线将以0.769m/d的速度扩散;在污染源得到有效治理和控制后,地下水污染物超标浓度等值线扩散速度将减少至0.402m/d,可见污染源治理对减缓地下水污染的扩散有重要作用。预测结果可作为选择地下水保护方案和污染治理措施的依据。      

污染场地六价铬迁移转化机制与数值模拟研究

随着全球工业化迅猛发展,土壤和地下水六价铬污染日益严重。基于某铁合金厂铬渣场地现场调查与采样分析,开展铬渣场地土样吸附、渗透和弥散试验,研究六价铬在粉质黏土土样中的吸附特性和迁移规律,建立考虑对流-弥散-吸附的六价铬迁移三维动力学模型,结合数值软件获取污染源位于场地上、下游时地下水中六价铬迁移分布特征,并揭示弥散度?和分配系数 对六价铬时空分布的影响。试验结果表明,粉质黏土对六价铬吸附符合Langmuir等温吸附模型,最大吸附量为466.6 mg/kg;蒸馏水和160 mg/L 六价铬溶液入渗下粉质黏土渗透系数约为6.5×10–7～6.7×10–7 cm/s,1 000 mg/L六价铬溶液的渗透系数增大至4.4×10–6 cm/s;粉质黏土水动力弥散系数D为1.4×10–4 m2/d,计算得到阻滞因子 为4.2～10。数值模拟结果表明,场地下游受到六价铬污染时,即使不考虑分子扩散作用,上游仍有被污染的风险,污染程度取决于含水层的弥散度;考虑含水层对六价铬吸附时,土体分配系数越大,六价铬污染羽分布范围越小,在预测地下水中六价铬浓度分布时应重点考虑六价铬吸附等转化过程。     

用镭同位素评价海水滞留时间及海底地下水排泄

海底地下水排泄(submarine groundwater discharge, SGD)难以直接测量, 镭同位素和氡-222等天然示踪剂使得间接评价SGD通量成为可能.为了评价五缘湾的水体滞留时间和SGD通量, 实测了湾内海水、湾外海水和地下水中224Ra和226Ra的活度, 利用224Ra和226Ra半衰期的差异, 采用224Ra与226Ra的活度比值计算湾内水团的年龄和平均滞留时间, 利用224Ra和226Ra的质量平衡模型计算SGD通量.五缘湾13个站位的水团年龄在0.6~2.4 d之间, 湾顶水团年龄相对较大, 平均海水滞留时间1.4 d.地下水输入五缘湾的224Ra和226Ra通量分别为5.17×106 Bq/d和5.28×106 Bq/d, 将该通量用地下水端元的活度转换成为SGD通量分别是0.21 m3/m2/d(224Ra平衡模型)和0.23 m3/m2/d(226Ra平衡模型), 两种模型的结果较接近, 其平均值0.22 m3/m2/d可作为五缘湾的海底地下水排泄通量.      

利用δ53Cr定量评价Cr(VI)还原程度的实验研究

地下水污染的原位修复是当今国际上净化地下水最具发展前景的新技术,但对铬污染地下水原位修复尚未有科学有效的评价方法。定量评价地下水中Cr(Ⅵ)的被还原程度成为保护与修复铬污染地下水的关键问题。通过室内Cr(Ⅵ)的还原实验,分析Cr(Ⅵ)在还原过程中铬稳定同位素变化规律,研究其分馏机理,探索利用铬同位素定量评价地下水中Cr(Ⅵ)还原程度的可行性。研究结果表明:Cr(Ⅵ)在被还原成Cr(Ⅲ)过程中,发生明显的同位素分馏,即反应物中53Cr逐渐富集,同时生成物中52Cr逐渐富集;分馏过程可用瑞利分馏模型描述,分馏系数α为常数0.99842。表明δ53Cr能够定量评价水体中Cr(Ⅵ)的还原程度,为评价地下水铬污染修复提供了新途径。     

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.     

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.     

含水介质对地下水污染曝气修复的影响

为进一步研究地下水曝气原位修复技术的影响因素,采用室内实验的方法系统地研究了含水介质对原位曝气技术修复地下水污染的影响。研究结果表明:大量水相中的柴油在曝气的开始阶段被去除,随着时间的延长,污染物去除率不断增加,但增加的幅度逐渐减小。污染物去除率与时间关系曲线符合对数曲线规律,相关方程为y=alnx+b,R2=0.802 4～0.907 1,相关性较好。含水介质的渗透系数对地下水污染修复的影响较大,渗透系数与污染物的去除率基本呈正相关关系,渗透系数越大,污染物的去除率越大;含水介质密度与污染物去除率基本呈负相关关系,含水介质密度越大,污染物的去除率越小。     

铬污染土壤和地下水的修复技术研究进展

上海20世纪70年代含铬废水排放量大,其中六价铬毒性大、溶解度高、迁移性强,极易随水淋溶污染地下水系统。开展高效、经济的土壤和地下水中铬污染修复方法的研究,具有重要的现实意义。本文系统地综述了铬污染场地修复技术现状,包括还原稳定、渗透反应墙、电动修复、生物修复等,重点探讨了上海地区污染深度大于4m的低渗透性的铬污染场地电动反应墙联合修复技术的发展趋势。     

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.     

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。     

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.     

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.      

Groundwater flow and capture zone analysis of the Central Passaic River Basin, New Jersey

Delineating capture zones of pumping wells is an important part of safe drinking water and well protection programs. Capture zones or contributing areas of a groundwater extraction well are the parts of the aquifer recharge areas from which the wells draw their water. Their extent and location depend on the hydrogeologic conditions such as groundwater recharge, pumping scenario and the aquifer properties such as hydraulic conductivity, porosity, heterogeneity of the medium and hydraulic gradient. Different methods of delineation can be used depending on the complexity of the hydrogeologic conditions. In this study, a 3-dimensional transient numerical MODFLOW model was developed for the Central Passaic River Basin (CPRB), and used with a MODPATH particle tracking code to determine 3-dimensional transient capture zones. Analytically calculated capture zones from previous studies at the site were compared with the new numerically simulated capture zones. The study results revealed that the analytical solution was more conservative, estimating larger capture zones than the numerical models. Of all the parameters that can impact the size, shape and location of a capture zone, the hydraulic conductivity is one of the most critical. Capture zones tend to be smaller in lower hydraulic conductivity areas.