Feasibility Evaluation of Using Biochar-based Permeable Reactive Barrier for the Remediation of Mercury and Arsenic Composite Polluted Water Bodies

This study employed a modified biochar material to construct a permeable reactive barrier(PRB)for the treatment of water bodies polluted with mercury and arsenic.The experimental results demonstrated that the addition of goethite-modified biochar significantly enhanced the remediation efficiency of As(III),achieving a maximum removal rate of 100%.Conversely,pure biochar exhibited high efficiency in the removal of Hg(II),with a maximum removal rate approaching 100%.Furthermore,the pH level of the water significantly influenced the adsorption efficiency of heavy metal ions,with the optimal removal performance observed at a pH of 6.0.The PRB system demonstrated excellent removal rates under low concentrations of heavy metals.However,as the concentration increased,the remediation efficiency exhibited a slight decrease.In summary,the findings of this study provide compelling evidence for the use of modified biochar in the construction of PRBs for the remediation of mercury and arsenic-polluted water bodies.Furthermore,the study reveals the mechanism by which pH and heavy metal concentration influence remediation efficiency.

Performance of Metal and Acid Ions Remediation in Contaminated Soils by Electrokinetics with Chitosan Permeable Reactive Barrier

Metal and acid ions contamination of soil in China is serious. To find an efficient solution for remediating the combined pollution,electrokinetics( EK) coupled with chitosan( CTS)permeable reactive barrier( EK/CPRB) was used to investigate the performances of metal and acid ions remediation. Adsorption characteristics of Zn^(2+),Fe^(3+),Ca^(2+),SO_4^(2-) and NO_3^- onto CTS were also conducted. The results showed the sorption of Zn^(2+),Fe^(3+),Ca^(2+),SO_4^(2-) and NO_3^- on CTS could be well described by Freundlich model. When the CTS dosage is 8 g,the total removal efficiency for Zn^(2+),Fe^(3+),Ca^(2+),SO_4^(2-) and NO_3^- is 86. 8%,90. 2%,92. 4%,90. 0% and 82. 5%,respectively. CTS enhanced ions remediation efficiencies significantly compared with the single EK system,especially for SO_4^(2-) and NO_3^-. The results indicate EK/CPRB system is suitable for the remediation of soil contaminated by both metal ions and acid ions.

Pilot Test of the Permeable Reactive Barrier for Removing Uranium from the Flooded Gunnar Pit

This work reports on applying iron oxide coated sand (IOCS) media in an experimental permeable reactive barrier to remove uranium (U) species from uranium containing water. A field study was conducted at the legacy Gunnar uranium mine & mill site that was abandoned in the 1960s with limited to no decommissioning. The flooded Gunnar mine pit presently contains about 3.2 million m3 of water contaminated by dissolved U (1.2 mg/L), Ra-226 (0.4 Bq/L), and minor concentrations of other contaminants (As, Se, etc.). The water is seeping over the pit rim into Lake Athabasca, posing potential environmental and health concerns. IOCS media can be used to immobilize uranium species through an adsorption process. Herein, the preparation of hydrous ferric oxide sorbents and their supported forms onto silica sands is described. Fourier transform infrared spectroscopy (FTIR) and powder X-ray diffraction (pXRD) were used for structural characterization. The adsorption properties of the IOCS sorbent media were modeled by the Langmuir adsorption isotherm, where a maximum uranium uptake capacity was estimated. Bench-scale adsorption kinetic experiments were also performed before moving to a field trial. Based on these lab results and input on field-scale parameters, a pilot permeable reactive barrier was fabricated and a field test conducted near the Gunnar pit in June 2019. This pilot test provided technical data and information needed for designing a full-scale permeable barrier that employs the IOCS media. This approach can be applied for in-situ water treatment at Gunnar and other legacy uranium sites.

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.

PRB处理酸性矿山废水的地球化学反应模拟研究

随着工业的迅速发展,矿产资源的需求也随之增加,采矿过程中产生的酸性矿山废水(Acid Mine Drainage,AMD)对周围环境具有严重危害性,可渗透反应墙(Permeable Reactive Barrier,PRB)通过下放置反应材料,利用自然水力梯度拦截污染羽流,该技术已成为有效处理AMD的手段之一。为研究PRB内化学反应堵塞对其处理效果的影响,搭建了规模为60 cm×15 cm×20 cm的箱体装置,模拟石灰石PRB处理AMD的过程;基于箱体实验得到的数据,并利用化学反应输运模型理论开发了一种新的地球化学算法,来描述PRB处理AMD过程中可能会发生的化学反应,最后通过MODFLOW和RT3D的耦合模拟并预测PRB有效处理污染物质的最大寿命。结果表明:①有效地模拟出了PRB中石灰石的酸性中和能力及其对酸性废水中总铁、Al^(3+)的去除效果,并且很好地反映出PRB系统的化学堵塞过程;②模拟结果与实测值吻合程度较好。进口区域、中间区域以及出口区域3个不同位置处出水的pH实测值与预测值的最大误差分别为0.38、0.30和0.29,总铁质量浓度实测值与预测值的最大误差分别为1.570、0.102和0.124 mg/L,Al^(3+)质量浓度实测值与预测值的最大误差分别为1.010、0.374和0.160 mg/L;③预测结果表明,该实验室规模的PRB装置在前30 d出水中的总铁和Al^(3+)质量浓度最低,去除效果最好,且去除能力随着时间逐渐减弱。参照地下水质量标准限制,判断出该石灰石PRB能够有效处理总铁的最大寿命为132 d,有效处理Al^(3+)的最大寿命为63 d。

Passive convergence-permeable reactive barrier (PC-PRB): An effective configuration to enhance hydraulic performance

A novel permeable reactive barrier(PRB)configuration,the so-called passive convergence-permeable reactive barrier(PC-PRB),is proposed to overcome several shortcomings of traditional PRB configurations,such as high dependency to site hydrogeological characteristics and plume size.The PC-PRB is designed to make the plume converge towards the PRB due to the passive hydraulic decompression-convergent flow effect.The corresponding passive groundwater convergence(PC)system is deployed upstream of the PRB system,which consists of passive wells,water pipes,and a buffer layer.A two-dimensional(2D)finite-difference hydrodynamic code,entitled PRB-Flow,is developed to examine the hydraulic performance parameters(i.e.,capture width(W)and residence time(t))of PC-PRB.It is proved that the horizontal 2D capture width(Wh)and vertical 2D capture depth(Wv)of the PC-PRB remarkably increase compared to that of the continuous reactive barrier(C-PRB).The aforementioned relative growth values in order are greater than 50%and 25%in this case study.Therefore,the PRB geometric dimensions as well as the materials cost required for the same plume treatment lessens.The sensitivity analysis reveals that the dominant factors influencing the hydraulic performance of the PC-PRB are the water pipe length(Lp),PRB length(LPRB),passive well height(Hw),and PRB height(HPRB).The discrepancy between the Wh of PC-PRB and that of the C-PRB(i.e.,∆Wh)has a low correlation with PRB parameters and mainly depends on Lp,which could dramatically simplify the PC-PRB design procedure.Generally,the proposed PC-PRB exhibits an effective PRB configuration to enhance hydraulic performance.

基于EK−PRB修复镉污染土壤的微生物优化技术

采用电动-可渗透反应墙(EK-PRB)联合微生物优化技术,研究其对Cd污染土壤修复效果的影响。利用固定化微生物技术,制备粉煤灰-酵母菌小球、壳聚糖-酵母菌小球和生物炭-酵母菌小球,并对比制备的PRB小球和单一的PRB材料(粉煤灰、生物炭、壳聚糖)对Cd去除效果的影响。结果表明,相对于单一的PRB材料,PRB小球可增加土壤中的电流和电导率,对Cd的去除率更高,但是对pH影响较小。通过对PRB材料进行表征分析,证实了其对Cd去除效果有一定影响。考虑到经济成本与修复效果,选择电压梯度为2.5 V·cm^(-1),PRB材料为粉煤灰-酵母菌小球去除Cd,去除率可达53.70%。研究结果证实了固定化微生物结合EK-PRB技术的可行性以及修复优势。

非正规生活垃圾填埋场污染地下水修复的PRB反应介质试验研究

我国存在大量的非正规生活垃圾填埋场,由于它们在运行之前没有采取严格的防渗防污措施,垃圾渗滤液下渗导致当地地下水严重污染。地下水污染原位修复技术中的渗透性反应墙(PRB)技术由于其运行成本低、能长期有效运行、不影响生态环境等优点已得到广泛应用。以湖北省石首市某非正规生活垃圾填埋场渗滤液污染的地下水为研究对象,通过静态批次试验,探索了PRB单一反应介质类型、反应温度、单一反应介质投加量、复合反应介质配比对污染地下水的修复效果,并通过SEM、XRD、FT-IR对不同反应介质的污染物去除机理进行了讨论。结果表明:3种单一反应介质即海藻酸钠(SA)-聚乙烯醇(PVA)包裹微球、生物炭和聚合氯化铝(PAC)-阳离子聚丙烯酰胺(C-PAM)改性膨润土对污染地下水中六价铬、氨氮、COD、总磷的最大去除率分别为99.96%、98.97%、88.58%、99.20%;在研究区地下水温度变化范围内,温度对单一反应介质去除污染物性能的影响不大;单一反应介质投加量对六价铬、氨氮和总磷最终去除率的影响不大,仅对COD的去除效果有影响,反应时间为120 h时1 g/100 mL的单一反应介质投加量下污染地下水中COD的去除率为88.58%,3 g/100 mL和5 g/100 mL的单一反应介质投加量下对COD的去除率均可达98.42%;按照3种单一反应介质2∶1∶1的质量比制备的复合反应介质,反应时间为120 h时其对污染地下水中六价铬、氨氮、COD、总磷的去除率分别为99.61%、96.03%、81.25%、99.20%。该研究结果可为研究区利用PRB技术修复非正规生活垃圾填埋场渗滤液污染的地下水提供理论依据。

Woodchip-sulfur packed biological permeable reactive barrier for mixotrophic vanadium(V)detoxification in groundwater

Groundwater vanadium(V)(V(V))contamination is ubiquitous in vanadium mining/smelting region and development of novel strategy for its remediation is of particular significance.Herein woodchip-sulfur packed biological permeable reactive barrier(bio-PRB)is established towards successful V(V)bio-detoxification.V(V)removal was accelerated under such mixotrophic condition,compared with heterotrophic and autotrophic V(V)reductions.The performance of bio-PRB was relatively steady with V(V)removal efficiency of 68.5%–98.2%under fluctuant geochemical and hydrodynamic conditions.Microbial community analysis indicated that heterotrophic Geobacter was the main reducer to convert V(V)to insoluble V(IV),by consumption of organic source attributed to woodchip hydrolysis and sulfur anabolism of autotrophs(e.g.,Sulfuricurvum and Thiobacillus).V(V)reduction and elemental sulfur oxidation were regulated by genes as omcA,omcB and mtrC and soxB,respectively.The elevated contents of cytochrome c and nicotinamide adenine dinucleotide implied that improved electron transfer facilitated V(V)reduction.This study provides a cost-effective,robust and sustainable route for V(V)-polluted aquifer remediation.

Nitrate Removal by a Permeable Reactive Barrier of Fe0:A Model-Based Evaluation

Permeable reactive barrier（PRB） filled with zero valent iron（ZVI, Fe0） can be an effective option to remove nitrate from contaminated groundwater. The long-term performance of such PRBs, however, might be compromised by the problem of declining reactivity and permeability, which could cause a decrease in the nitrate removal efficiency. In this study we explored suitable model formulations that allow for a process-based quantification of the passivation effect on denitrification rates and tested the model for a 40 years long operation scenario. The conceptual model underlying our selected formulation assumes the declining reactivity of the ZVI material through the progressing passivation caused by the precipitation of secondary minerals and the successive depletion of the ZVI material. Two model scenarios, i.e., the base model scenario which neglects the explicit consideration of the passivation effect and one performed with the model in which the impact of the passivation effect on denitrification was considered, were compared. The modeling results illustrate that nitrate removal in the model of considered passivation started to be incomplete after 10 years, and the effluent nitrate concentration of PRB rose up to 86% of the injected water concentration after 40 years, in contrast to the base scenario, corresponding well with the field observations of successively declining nitrate removal efficiencies. The model results also showed that the porosity of the PRB increased in both models. In order to improve and recover the reactivity of ZVI, pyrite was added to the PRB, resulting in completely nitrate removal and lower consumption of ZVI.

零价铁PRB技术在地下水原位修复中的研究进展

PRB(可渗透反应墙)是地下水治理中新型的原位修复技术,具有成本低、处理效果好、对环境干扰小等优点,已逐渐应用到实际.原位修复技术中PRB根据结构的不同可分为单处理系统PRB和多单元处理系统PRB,单处理系统PRB适用于单一污染物、污染浓度较低、污染羽规模较小的场地,多单元系统用于污染场地较复杂、污染种类较多的场地.零价铁PRB去除地下水中无机污染物及有机组分的反应机理主要是氧化还原反应和还原性脱卤反应.实际场地PRB的运行中存在的主要问题是零价铁钝化及PRB堵塞,现阶段的解决方法主要包括超声、电化学等,但为了提高PRB技术的实用性,铁材料的解钝化技术、实际场地PRB的设计与安装、PRB体系的长期运行及服务期满后的处置均需进一步的研究探索.

用双层PRB技术处理垃圾填埋场地下水污染的可行性研究

设计了双层结构可渗透反应屏障(PRB),对渗滤液污染地下水原位处理的可行性进行实验研究.其中,第一反应器主要填充了零价铁,对复杂的不可生物降解和难生物降解的卤代烃等有机物进行分解;第二反应器主要填充了释氧剂(ORC),对有机物进行彻底的处理.实验结果表明:经过第一反应器后BOD5 COD值由0 32升高至0 75,铵离子和硝酸根离子的去除率分别达到85%和80%;ORC反应器最大释氧量为7 64mg·L-1.采用双层PRB结构治理渗滤液污染地下水是可行的.

PRB修复垃圾渗滤液污染地下水过程中pH值变化分析

随着城市化的不断发展,生活垃圾产生量越来越多,因管理不善,导致垃圾渗滤液污染地下水的问题越来越突出,污染地下水的修复研究迫在眉睫。实验模拟地下环境,以被垃圾渗滤液污染地下水为研究对象,分别用沸石、无烟煤、陶粒、活性炭、炉渣、粉煤灰、零价铁作为反应介质,设计了6种地下可渗透反应墙(PRB),分别为反应器1、2、3、4、5和6。分3个阶段对PRB技术治理污染地下水中pH值影响和变化进行模拟研究,分析反应器pH值降低的原因并探讨pH值变化机理。实验结果表明,所有反应器pH值较进口降低,第三阶段出口pH值平均值较进口平均降低0.40;因水解酸化反应存在,产生一定量NH4+和有机酸,造成反应器出水pH值降低和复合填充材料NH4+相对去除率降低,说明PRB技术治理渗滤液污染地下水具有一定可行性,但技术方法有待继续深入研究。

PRB技术处理污染地下水的试验研究

试验采用粗砂、零价铁、富含微生物的土壤和锯末按不同比例搅拌均匀形成混合物，以此为介质做成可渗透反应墙（Permeable Reactive Barrier，简称PRB）反应器；取大通垃圾场产生的垃圾渗滤液，分别稀释5倍和40倍制成水样，作为模拟污染的地下水；进行2组正交试验，对各反应器的综合处理效果进行对比分析，结果表明：地下水中污染物的含量增高时，PRB出水pH值的增幅也会随之增大；进水污染物浓度变化时同一反应器CODcr去除率、BOD5去除率差异均很大，部分反应器CODcr和BOD5去除率在50％以上，但也有反应器出水CODcr和BOD5不降反升；2组正交试验的浊度去除率都处在较高的水平，许多反应器浊度去除率达到了80％～90％；进水浓度低时反应器的色度去除率超过70％。因此，用PRB处理受垃圾渗滤液污染的地下水是可行的。同时，从正交试验结果也得出了进水污染物浓度不同时PRB的最佳介质配比、反应时间以及各影响因素的丰次排序，为PRB讲一步的研究和设计提供了依据．

堆肥-零价铁混合PRB处理铬污染地下水

分别用堆肥、零价铁、堆肥-零价铁作为反应介质,对PRB处理铬污染地下水的可行性和有效性进行了研究。结果表明:以堆肥-零价铁作为反应介质的反应柱去除Cr(Ⅵ)的效果比单独以堆肥或铁粉为介质的反应柱好;增加铁粉或堆肥的用量均有利于Cr(Ⅵ)的去除;堆肥时间对Cr(Ⅵ)的去除效果影响不大;出水总铁含量符合《生活饮用水卫生标准》要求。

PRB在地下水污染修复中的应用与研究进展

地下水污染已成为当今世界严峻的环境问题。为保护地下水资源,采取有效的地下水污染防治措施已迫在眉睫。PRB作为原位治理领域中的新型技术,具有处理时效长、可同时处理多种污染物、运行费用低等优点。综述了PRB的结构类型、反应介质、反应机理和国内外研究进展,分析了存在的问题,并对其应用前景进行了展望。

PRB连续反应单元模拟与敏感性分析

根据PRB原理,考虑对流作用、弥散作用、吸附作用、化学反应等因素对溶质运移的影响,设计了连续反应单元.结果表明,对流作用对溶质运移速度影响较大,吸附作用与化学反应对污染物的去除影响较大.分析了地下含水层水力传导系数(Kaquifer)及连续反应单元内的水力传导系数(Kcell)对溶质运移的影响.结果表明,地下含水层Kaquifer较小(Kaquifer为1和5 m/d)时,Kcell取值对溶质运移总量影响不大;当Kcell∶Kaquifer≥10时,增加Kcell值对促进溶质运移作用较小.

零价铁PRB修复硝酸盐和铬复合污染地下水

通过连续流动试验研究了Fe0(零价铁)-PRB(渗透反应格栅)修复受NO3--N、Cr(Ⅵ)以及NO3--N和Cr(Ⅵ)复合污染模拟地下水的反应特性,分析了Fe0对NO3--N和Cr(Ⅵ)的氧化还原产物,并且对NO3--N和Cr(Ⅵ)的相互影响进行了研究.采用粒径为0.15～0.42 mm的Fe0和粒径为0.15 mm的活性炭作为PRB反应介质,二者的质量比为1∶1.结果表明,Fe0单独与NO3--N反应情况下,当进水中ρ(NO3--N)为20 mg/L时,去除率达95%,NO2-为还原过渡状态,NH4+是主要产物,出水pH从原水的7.1升至9.0左右,出水中ρ(TFe)<0.60 mg/L.Fe0处理Cr(Ⅵ)情况下,对Cr(Ⅵ)有较高的去除效果,进水中ρ〔Cr(Ⅵ)〕为10 mg/L时,去除率达96%,反应产物Fe3+和Cr(Ⅲ)可以形成沉淀附着在反应介质上,不会迁移到"下游"水体中,出水pH从原水的7.0升至8.0左右,出水中ρ(TFe)<0.30 mg/L.Fe0去除NO3--N和Cr(Ⅵ)复合污染时,共存的NO3--N对Cr(Ⅵ)的去除效果没有影响,Cr(Ⅵ)的存在降低了NO3--N的去除效果.

PRB修复渗滤液污染地下水的实验研究

可渗透反应墙(PRB)原位修复地下水污染技术,具有经济、高效等特点。采用PRB技术治理渗滤液污染的地下水,反应介质的选择和介质配比是一个关键问题。因此,以渗滤液污染地下水为研究对象,分别用零价铁粉、活性炭、沸石和陶粒4种混合介质,设计了5个PRB反应器,分别为A、B、C、D和E,对PRB修复渗滤液污染地下水的可行性和有效性进行了试验研究。设计的反应器充分考虑了反应器的渗透性能。实验结果表明:混合介质反应器A、B、C、D和E对CODcr的平均去除率分别达到了79.6%、75.6%、77.0%、78.9%和79.9%;对NH4+的平均去除率分别为87.3%、82.1%、92.1%、98.8%和88.5%。验证了PRB技术处理垃圾渗滤液对处理地下水污染的可行性。