Persulfate oxidation for in situ remediation of TCE. II. Activated by chelated ferrous ion

In situ chemical oxidation (ISCO) is a technique used to remediate contaminated soil and groundwater systems. It has been postulated that sodium persulfate (Na2S2O8) can be activated by transition metal ions such as ferrous ion (Fe2+) to produce a powerful oxidant known as the sulfate free radical (SO4-*) with a redox potential of 2.6 V, which can potentially destroy organic contaminants. In this laboratory study persulfate oxidation of dissolved trichloroethylene (TCE) was investigated in aqueous and soil slurry systems under a variety of experimental conditions. A chelating agent (i.e., citric acid) was used in attempt to manipulate the quantity of ferrous ion in solution by providing an appropriate chelate/Fe2+ molar ratio. In an aqueous system a chelate/Fe2+ molar ratio of 1/5 (e.g., S2O8(2)-/chelate/Fe2+/TCE ratio of 20/2/10/1) was found to be the lowest acceptable ratio to maintain sufficient quantities of Fe2+ activator in solution resulting in nearly complete TCE destruction after only 20 min. The availability of Fe2+ appeared to be controlled by adjusting the molar ratio of chelate/Fe2+. In general, high levels of chelated ferrous ion concentrations resulted in faster TCE degradation and more persulfate decomposition. However, if initial ferrous ion contents are relatively low, sufficient quantities of chelate must be provided to ensure the chelation of a greater percentage of the limited ferrous ion present. Citric acid chelated ferrous ion appeared effective for TCE degradation within soil slurries but required longer reaction times. Additionally, the use of citric acid without the addition of supplemental Fe2+ in soil slurries, where the citric acid apparently extracted native metals from the soil, appeared to be somewhat effective at enhancing persulfate oxidation of TCE over extended reaction times. A comparison of different chelating agents revealed that citric acid was the most effective.     

Metal mobility during in situ chemical oxidation of TCE by KMnO4

The potential for trace-metal contamination of aquifers as a side effect of In Situ Chemical Oxidation (ISCO) of chlorinated solvent contamination by KMnO(4) is investigated with column experiments. The experiments investigate metal mobility during in situ chemical oxidation of TCE by KMnO(4) under conditions where pH, flow rate, KMnO(4), TCE, and trace-metal concentrations were controlled. During ISCO, the injection of MnO(4) creates oxidizing conditions, and acidity released by the reactions causes a tendency toward low pH in aquifers. In order to evaluate the role of pH buffering on metal mobility, duplicate columns were constructed, one packed with pure silica sand, and one with a mixture of silica sand and calcite. Aqueous solutions of TCE and KMnO(4) (with 1 mg/L Cu, Pb, Zn, Mo, Ni, and Cr(VI)) were allowed to mix at the inlet to the columns. After the completion of the experiments, samples of Mn oxide were removed from the columns and analyzed by analytical scanning and transmission electron microscopy. In order to relate the results of the laboratory experiments to field settings, the analyses of Mn-oxide samples from the lab experiments were compared to samples of Mn oxide collected from a field-scale chemical-oxidation experiment that were also analyzed by analytical electron microscopy as well as time-of-flight secondary-ion mass spectroscopy. The pH ranged from 2.40 in the silica sand column to 6.25 in the calcite-containing column. The data indicate that aqueous Mo, Pb, Cu and Ni concentrations are attenuated almost completely within the columns. In contrast, Zn concentrations are not significantly attenuated and Cr(VI) is transported conservatively. The results indicate that within the range 2.40 to 6.25, metal mobility is not affected by pH. Comparison of analyses of Mn-oxide from the lab and field demonstrate that a variety of metals are sequestered from solution by Mn oxide.     

Persulfate oxidation of trichloroethylene with and without iron activation in porous media

In situ chemical oxidation with persulfate anion (S2O82*) is a viable technique for remediation of groundwater contaminants such as trichloroethylene (TCE). An accelerated reaction using S2O82* to destroy TCE can be achieved via chemical activation with ferrous ion to generate sulfate radicals (SO4*)(E degrees =2.6 V). The column study presented here simulates persulfate oxidation of TCE in porous media (glass beads and a sandy soil). Initial experiments were conducted to investigate persulfate transport in the absence of TCE in the column. The persulfate flushing exhibited a longer residence time and revealed a moderate persulfate interaction with soils. In TCE treatment experiments, the results indicate that the water or persulfate solution would push dissolved TCE from the column. Therefore, the effluent TCE concentration gradually increased to a maximum when about one pore volume was replaced with the flushing solution in the column. The presence of Fe2+ concentration within the column caused a quick drop in effluent TCE concentration and more TCE degradation was observed. When a TCE solution was flushing through the soil column, breakthrough of TCE concentration in the effluent was relatively slow. In contrast, when the soil column was flushed with a mixed solution of persulfate and TCE, persulfate appeared to preferentially oxidize soil oxidizable matter rather than TCE during transport. Hence, persulfate oxidation of soil organics may possibly reduce the interaction between TCE and soil (e.g., adsorption) and facilitate the transport of TCE through soil columns resulting in faster breakthrough.     

原位化学氧化法在土壤和地下水修复中的研究进展

综述了原位化学氧化法修复污染土壤及地下水的最新进展 ,着重介绍了几种氧化剂 ,如二氧化氯、双氧水及Fenton试剂、高锰酸钾和臭氧在土壤修复中的应用、不足及改进 ,并对化学氧化修复技术的发展前景进行了展望     

DNAPL remediation with in situ chemical oxidation using potassium permanganate. Part I. Mineralogy of Mn oxide and its dissolution in organic acids

Previous studies on in situ chemical oxidation of trichloroethylene (TCE) with potassium permanganate indicated that the solid reaction product, Mn oxide, could reduce the permeability of the porous medium and impact the success of dense non-aqueous phase liquid (DNAPL) removal. In order to address the issue of permeability reduction caused by precipitation, this study investigated the mineralogy of Mn oxides and the possibilities of removing the solid precipitates by dissolution. The solid reaction product from the oxidation of TCE by permanganate is semi-amorphous potassium-rich birnessite, which has a layered mineral structure with an interlayer spacing of 7.3 A. The chemical formula is K(0.854)Mn(1.786)O(4).1.55H(2)O. It has a relatively small specific surface area at 23.6+/-0.82 m(2)/g. Its point of zero charge (pzc) was measured as 3.7+/-0.4. This birnessite is a relatively active species and could participate in various reactions with existing organic and inorganic matter. The dissolution kinetics of Mn oxide was evaluated in batch experiments using solutions of citric acid, oxalic acid, and ethylenediaminetetraacetic acid (EDTA). Initial dissolution rates were determined to be 0.126 mM/m(2)/h for citric acid, 1.35 mM/m(2)/h for oxalic acid, and 5.176 mM/m(2)/h for EDTA. These rates compare with 0.0025 mM/m(2)/h for nitric acid at pH=2. Organic acids dissolve Mn oxide quickly. Reaction rates increase with acid concentration, as tested with citric acid. The dissolution mechanism likely involves proton and ligand-promoted dissolution and reductive dissolution. Citric and oxalic acid can induce ligand-promoted dissolution, while EDTA can induce ligand-promoted and reductive dissolutions. At low pH, proton-promoted dissolution seems to occur with all the acids tested, but this process is not dominant. Reductive dissolution appears to be the most effective process in dissolving the solid, followed by ligand-promoted dissolution. These experiments indicate the significant potential in using these organic acids to remove precipitates formed during the oxidation reaction.     

DNAPL remediation with in situ chemical oxidation using potassium permanganate. II. Increasing removal efficiency by dissolving Mn oxide precipitates

In situ chemical oxidation (ISCO) schemes using MnO4- have been effective in destroying chlorinated organic solvents dissolved in ground water. Laboratory experiments and field pilot tests reveal that the precipitation of Mn oxide, one of the reaction products, causes a reduction of permeability, which can lead to flow bypassing and inefficiency of the scheme. Without a solution to this problem of plugging, it is difficult to remove DNAPL from the subsurface completely. In a companion paper, we showed with batch experiments that Mn oxide can be dissolved rapidly with certain organic acids. This study utilizes 2-D flow-tank experiments to examine the possibility of nearly complete DNAPL removal by ISCO with MnO4-, when organic acids are used to remove Mn oxide. The experiments were conducted in a small 2-D glass flow tank containing a lenticular silica-sand medium. Blue-dyed trichloroethylene (TCE) provided residual, the perched and pooled DNAPL. KMnO4 at 200 mg/l was flushed through the DNAPL horizontally. Once plugging reduced permeability and prevented further delivery of the oxidant, citric or oxalic acids were pumped into the flow tank to dissolve the Mn oxide precipitates. Organic ligands removed the Mn oxide precipitates relatively quickly, and permitted another cycle of MnO4- flooding. Cycles of MnO4-/acid flooding continued until all of the visible DNAPL was removed. The experiments were monitored with chemical analysis and visualization. A mass-balance calculation indicated that by the end of the experiments, all the DNAPL was removed. The results show also how heterogeneity adds complexity to initial redistribution of DNAPL, and to the efficiency of the chemical flooding.     

Manganese and trace-metal mobility under reducing conditions following in situ oxidation of TCE by KMnO4: a laboratory column experiment

The stability of Mn oxides, and the potential for mobilization of associated trace metals, were assessed by simulating the onset of microbially-mediated reducing conditions in a continuous-flow column experiment. The column had previously been used for an in situ chemical oxidation (ISCO) experiment in which trichloroethylene was reacted with permanganate in the presence of aqueous trace metals, which produced Mn oxyhydroxides (MnO(x)) that sequestered the trace metals and coated the column sand. The column influent solution represented the incursion of ambient groundwater containing dissolved organic carbon (DOC) into an ISCO treatment zone. The influx of DOC-containing groundwater initiated a series of cation-exchange, surface-complexation and reductive-dissolution reactions that controlled the release of aqueous metals from the system. Peak concentrations in the effluent occurred in the order Na, Mo, Cr, Zn, K, Mn, Fe, Pb, Mg, Ni, Cu and Ca. Manganese release from the column was controlled by a combination of cation exchange, reductive dissolution and precipitation of rhodochrosite. The trend in Fe concentrations was similar to that of Mn, and also resulted from a combination of reductive dissolution and cation exchange. Cation exchange and/or surface-complexation were the primary mechanisms controlling Cu, Ni, Mo and Pb release to solution, while Zn and Cr concentrations did not display coherent trends. Although metal release from the treatment zone was evident in the data, concentrations of trace metals remained below 0.05 mg L(-1) with the exception of Mo which reached concentrations on the order of 1 mg L(-1). The establishment of anaerobic conditions in ISCO-treated aquifers may result in a prolonged flux of aqueous Mn(II), but with the exception of MoO(4)(2-), it is unlikely that trace metals sequestered with MnO(x) during ISCO will be released to the groundwater in elevated concentrations.     

Degradation of bisphenol A in aqueous solution by persulfate activated with ferrous ion

Degradation of bisphenol A (BPA) in aqueous solution was studied with high-efficiency sulfate radical (SO₄ ^?·), which was generated by the activation of persulfate (S₂O₈ ^2?) with ferrous ion (Fe²⁺). S₂O₈ ^2? was activated by Fe²⁺ to produce SO₄ ^?·, and iron powder (Fe⁰) was used as a slow-releasing source of dissolved Fe²⁺. The major oxidation products of BPA were determined by liquid chromatography-mass spectrometer. The mineralization efficiency of BPA was monitored by total organic carbon (TOC) analyzer. BPA removal efficiency was improved by the increase of initial S₂O₈ ^2? or Fe²⁺ concentrations and then decreased with excess Fe²⁺ concentration. The adding mode of Fe²⁺ had significant impact on BPA degradation and mineralization. BPA removal rates increased from 49 to 97 % with sequential addition of Fe²⁺, while complete degradation was observed with continuous diffusion of Fe²⁺, and the latter achieved higher TOC removal rate. When Fe⁰ was employed as a slow-releasing source of dissolved Fe²⁺, 100 % of BPA degradation efficiency was achieved, and the highest removal rate of TOC (85 %) was obtained within 2 h. In the Fe⁰–S₂O₈ ^2? system, Fe⁰ as the activator of S₂O₈ ^2? could offer sustainable oxidation for BPA, and higher TOC removal rate was achieved. It was proved that Fe⁰–S₂O₈ ^2? system has perspective for future works.     

地下水曝气修复技术现场试验与应用研究进展

结合近年来国内外地下水曝气修复现场工程实践,对原位曝气的设计、操作和监测技术进行了全面的综述。对原位设计中的相关参数进行了整理分析,给出了合理取值范围,并探讨了不同场地条件下的应对方法。发展新的监测技术(如示踪技术、新型传感器等)能使曝气系统的工作性能得到更有效的监测,对于曝气修复工程现场监测新技术进行了系统的归纳和总结。此外,对现场曝气修复效果影响因素如污染物类型、曝气方式、曝气井数量、最大生物降解速率、土体孔隙率和含水层有机碳含量等进行了分析,以利于实际操作工艺的优化。最后对未来地下水曝气修复现场试验研究需开展的工作进行了展望。     

Intermediate-scale 2D experimental investigation of in situ chemical oxidation using potassium permanganate for remediation of complex DNAPL source zones

In situ chemical oxidation is a technology that has been applied to speed up remediation of a contaminant source zone by inducing increased mass transfer from DNAPL sources into the aqueous phase for subsequent destruction. The DNAPL source zone can consist of one or more individual sources that may be present as an interconnected pool of high saturation, as a region of disconnected ganglia at residual saturation, or as combinations of these two morphologies. Potassium permanganate (KMnO(4)) is a commonly employed oxidant that has been shown to rapidly destroy DNAPL compounds like PCE and TCE following second-order kinetics in an aqueous system. During the oxidation of a target DNAPL compound, or naturally occurring reduced species in the subsurface, manganese oxide (MnO(2)) solids are produced. Research has shown that these manganese oxide solids may result in permeability reductions in the porous media thus reducing the ability for oxidant to be transported to individual DNAPL sources. It can also occur at the DNAPL-water interface, decreasing contact of the oxidant with the DNAPL. Additionally, MnO(2) formation at the DNAPL-water interface, and/or flow-bypassing as a result of permeability reductions around the source, may alter the mass transfer from the DNAPL into the aqueous phase, potentially diminishing the magnitude of any DNAPL mass depletion rate increase induced by oxidation. An experiment was performed in a two-dimensional (2D) sand-filled tank that included several discrete DNAPL source zones. Spatial and temporal monitoring of aqueous PCE, chloride, and permanganate concentrations was used to relate changes in mass depletion of, and mass flux, from DNAPL residual and pool source zones to chemical oxidation performance and MnO(2) formation. During the experiment, permeability changes were monitored throughout the 2D tank and these were related to MnO(2) deposition as measured through post-oxidation soil coring. Under the conditions of this experiment, MnO(2) formation was found to reduce permeability in and around DNAPL source zones resulting in changes to the overall flow pattern, with the effects depending on source zone configuration. A pool with little or no residual around it, in a relatively homogeneous flow field, appeared to benefit from resulting MnO(2) pore-blocking that substantially reduced mass transfer from the pool even though there was relatively little PCE mass removed from the pool. In contrast, a pool with residual around it (in a more typical heterogeneous flow field) appeared to undergo increased mass transfer as MnO(2) reduced permeability, altering the water flow and increasing the mixing at the DNAPL-water interface. Further, the magnitude of increased PCE mass depletion during oxidation appeared to depend on the PCE source configuration (pool versus ganglia) and decreased as MnO(2) was formed and deposited at the DNAPL-water interface. Overall, the oxidation of PCE mass appeared to be rate-limited by the mass transfer from the DNAPL to aqueous phase.     

Bench-scale visualization of DNAPL remediation processes in analog heterogeneous aquifers: surfactant floods and in situ oxidation using permanganate

We have conducted well-controlled DNAPL remediation experiments within a 2-D, glass-walled, sand-filled chamber using surfactants (Aerosol MA and Tween 80) to increase solubility and an oxidant (permanganate) to chemically degrade the DNAPL. Initial conditions for each remediation experiment were created by injecting DNAPL as a point source at the top of the chamber and allowing the DNAPL to migrate downward through a water-filled, heterogeneous, sand-pack designed to be evocative of a fluvial depositional environment. This migration process resulted in the DNAPL residing as a series of descending pools. Lateral advection across the chamber was used to introduce the remedial fluids. Photographs and digital image analysis illustrate interactions between the introduced fluids and the DNAPL. In the surfactant experiments, we found that DNAPL configured in a series of pools was easily mobilized. Extreme reductions in DNAPL/water interfacial tension occurred when using the Aerosol MA surfactant, resulting in mobilization into low permeability regions and thus confounding the remediation process. More modest reductions in interfacial tension occurred when using the Tween 80 surfactant resulting in modest mobilization. In this experiment, capillary forces remained sufficient to exclude DNAPL migration into low permeability regions allowing the excellent solubilizing properties of the surfactant to recover almost 90% of the DNAPL within 8.6 pore volumes. Injection of a potassium permanganate solution resulted in precipitation of MnO2, a reaction product, creating a low-permeability rind surrounding the DNAPL pools. Formation of this rind hindered contact between the permanganate and the DNAPL, limiting the effectiveness of the remediation. From these experiments, we see the value of performing visualization experiments to evaluate the performance of proposed techniques for DNAPL remediation.     

改性沸石去除地下水中铁锰实验研究

测定了2种改性沸石的基本特性,并选取0.6 m层高的交换柱,通过动态试验,研究其分别用于除铁和除锰的工艺性能。实验结果表明,2种沸石质量全交换容量分别为578.2 mmol/kg和722.2 mmol/kg;产水水质均能达到饮用水标准：含铁量≤0.3 mg/L,含锰量≤0.1 mg/L;减少进水中铁锰含量（≤2 mg/L）和降低运行流速（≤20 m/h）,都有利于提高工作交换容量,但流速对除铁沸石影响较小;再生剂为1 mol/L的NaCl,再生速率1 m/h条件下,每升除铁沸石再生剂用量为1.2 L,洗脱率（再生废液中目标离子含量与原水中过滤时的去除量之比）达0.95,比耗（再生剂用量与工作交换容量之比）为16,每升除锰沸石再生剂用量为1.6 L,洗脱率达0.8,比耗为16。     

Fe2+活化过硫酸钠原位修复氯苯污染地下水

通过建立土槽模型模拟实际污染场地,并采用Na2S2O8为氧化剂、柠檬酸螯合Fe2+为活化剂,研究了氯苯在地下水中的迁移分布规律、原位修复及其对地下水环境的影响。结果表明,氯苯在含水层水平纵向上的迁移作用大于横向迁移;随着时间的增加,地下水中氯苯浓度变化总趋势为先增加后减少并最终趋于稳定;随着迁移距离的增加,氯苯的浓度逐渐降低。柠檬酸螯合Fe2+活化Na2S2O8能够有效修复受氯苯污染的地下水和土壤;持续氧化36 h后,地下水和土壤中氯苯的去除率分别达到82.4%和80.3%。进一步研究发现,氧化处理后,出水的pH值基本稳定在3.5、SO42-浓度为88.7 mg/L,满足地下水Ⅱ类水质标准。     

The role of ferrous ion in Fenton and photo-Fenton processes for the degradation of phenol

The efficiency of different Fenton-related oxidative processes such as Fenton, solar-Fenton and UV-Fenton were examined using phenol as a model compound in simulated and industrial wastewater. A batch study was conducted to optimize parameters like pH, hydrogen peroxide concentration and ferrous ion concentration governing the Fenton process. At optimum conditions, different Fenton-related processes were compared for the degradation of phenol. Increased degradation and mineralisation efficiency were observed in photo-Fenton processes as compared to conventional Fenton process. The maximum mineralising efficiency for phenol with Fenton, solar and UV-Fenton processes were 41%, 96% and 97% respectively. In Fenton process, carboxylic acids like acetic acid and oxalic acid were formed as end products during the degradation of phenol while in photo-Fenton processes, both these ions were identified during the early stages of phenol degradation and were oxidized almost completely at 120 min of the reaction time. In photo-Fenton processes (solar and UV light) complete degradation were observed with 0.4 mM of Fe2+ catalyst as compared to 0.8 mM of Fe2+ in conventional Fenton process. In Fenton and solar-Fenton processes, an iron reusability study was performed to minimize the amount of iron used in treatment process. The efficacy of Fenton and solar-Fenton processes was applied to effluent from phenol resin-manufacturing unit for the removal and mineralisation of phenol.     

高锰酸钾修复PAHs污染土壤过程中Mn迁移转化规律

为探究高锰酸钾氧化修复技术应用过程中Mn元素迁移转化规律及其潜在的环境风险,通过室内模拟实验,采用某焦化厂PAHs污染土壤作为研究材料,探究了高锰酸钾修复技术中不同药剂投加量对PAHs去除、高锰酸钾消耗量、土壤中Mn质量分数、Mn赋存形态分布及有效态Mn质量分数等的影响。结果表明,高锰酸钾氧化处理可有效去除土壤中PAHs;当高锰酸钾投加量为0.20 mmol·g⁻¹、反应时间为1 d时,PAHs去除率最高,可达89.61%。氧化处理过程中,高锰酸钾消耗量和土壤Mn质量分数均与高锰酸钾的投加量有关,随投加量增加而升高。其中,土壤Mn的质量分数与高锰酸钾消耗量呈显著正相关关系。高锰酸钾氧化处理后土壤中Mn主要以铁锰氧化物结合态存在,所占比例为77.04%~92.17%。土壤经0.05 mmol·g⁻¹高锰酸钾氧化处理后,土壤有效态Mn的质量分数比对照组增加了0.94倍;而在高锰酸钾投加量为0.10~0.40 mmol·g⁻¹的处理条件下,土壤有效态Mn的质量分数下降了77.65%~99.09%。药剂投加量是影响高锰酸钾氧化修复PAHs污染土壤过程中Mn环境行为的关键因子。本研究结果可为高锰酸钾氧化修复技术应用工艺优化提供参考。     

In situ bioelectrokinetic remediation of phenol-contaminated soil by use of an electrode matrix and a rotational operation mode

In situ bioremediation is a safe and cost-effective technology for the cleanup of contaminated sites, but its remediation rate is usually very slow. This study attempted to accelerate the process of bioremediation by employing non-uniform electrokinetic transport processes to mix organic pollutants and degrading bacteria in soils under in situ conditions (namely, in situ bioelectrokinetic remediation) by use of an electrode matrix and a rotational operation mode. A bench-scale non-uniform electrokinetic system with periodic polarity-reversal was developed for this purpose, and tested by using a sandy loam spiked with phenol as a model organic pollutant. The results demonstrated that non-uniform electrokinetic processes could enhance the in situ biodegradation of phenol in the soil, the efficiency of which depended upon the operational mode of the electric field. Compared with the unidirectional operation and the bidirectional operation, the rotational operation could effectively stimulate the biodegradation of phenol in the soil if adopting appropriate time intervals of polarity-reversal and electrode matrixes. A reversal interval of 3.0 h and a square-shaped electrode matrix with four electrode couples appeared appropriate for the in situ biodegradation of phenol, at which a maximum phenol removal of 58% was achieved in 10d and the bioremediation rate was increased about five times as compared to that with no electric field applied. The results also showed that adopting a small polarity-reversal interval and an appropriate electrode array could produce a high and uniform removal of phenol from the soil. It is believed that in situ bioelectrokinetic remediation holds the potential for field application.     

硝酸钙缓释颗粒原位修复黑臭底泥的作用机制及其应用

为解决水体中沉积底泥的内源污染释放问题,亟需高效底泥修复技术。硝酸盐为底泥微生物的电子受体,可通过反硝化作用氧化底泥的黑臭物质,是极具潜力的底泥修复剂。为探明硝酸盐在实际工程中的修复效果和潜在问题,结合实验室模拟和实际修复工程,分析了投加硝酸钙颗粒对黑臭底泥原位修复的环境过程。结果表明,投加硝酸钙缓释颗粒产品能显著提高底泥氧化还原势能（以Fe(II)/Fe(III)表征）,促进黑臭物质转化,实际硫化物氧化率达85.2%,使得底泥由黑转黄,最终实现修复目标。同时,硝酸钙修复底泥的过程不受上覆水水质影响,且因修复过程消耗了大量底泥耗氧物质（硫化物和易降解有机质）,使水体整体复氧能力提高。另一方面,钙离子的加入使磷素以较为稳定的钙磷形态转化,能改变水相总磷的归趋（TP_SedCaN < TP_CK,p < 0.01）。然而,由于反硝化产气增加了底泥孔隙,增加了泥水界面表面积和污染物扩散通量,故在修复初期存在底泥污染物和硝酸盐向其浓度较低的水相扩散,产生了一定风险,而实际上这也有利于泥相污染物的加速释放。因此,建议在可控工程段,联合覆盖法阻断污染物扩散或联合曝气加速水相污染物氧化,以确保在控制风险的前提下达到最优的底泥修复效果。     

Field evaluation of in situ remediation of a heavy metal contaminated soil using lime and red-mud

We evaluated the effectiveness of lime and red mud (by-product of aluminium manufacturing) to reduce metal availability to Festuca rubra and to allow re-vegetation on a highly contaminated brown-field site. Application of both lime and red mud (at 3 or 5%) increased soil pH and decreased metal availability. Festuca rubra failed to establish in the control plots, but grew to a near complete vegetative cover on the amended plots. The most effective treatment in decreasing grass metal concentrations in the first year was 5% red mud, but by year two all amendments were equally effective. In an additional pot experiment, P application in combination with red mud or lime decreased the Pb concentration, but not total uptake of Pb in Festuca rubra compared to red mud alone. The results show that both red mud and lime can be used to remediate a heavily contaminated acid soil to allow re-vegetation.     

Modelling of geochemical and isotopic changes in a column experiment for degradation of TCE by zero-valent iron

Zero-valent iron (ZVI) permeable-reactive barriers have become an increasingly used remediation option for the in situ removal of various organic and inorganic chemicals from contaminated groundwater. In the present study a process-based numerical model for the transport and reactions of chlorinated hydrocarbon in the presence of ZVI has been developed and applied to analyse a comprehensive data set from laboratory-scale flow-through experiments. The model formulation includes a reaction network for the individual sequential and/or parallel transformation of chlorinated hydrocarbons by ZVI, for the resulting geochemical changes such as mineral precipitation, and for the carbon isotope fractionation that occurs during each of the transformation reactions of the organic compounds. The isotopic fractionation was modelled by formulating separate reaction networks for lighter ((12)C) and heavier ((13)C) isotopes. The simulation of a column experiment involving the parallel degradation of TCE by hydrogenolysis and beta-elimination can conclusively reproduce the observed concentration profiles of all collected organic and inorganic data as well as the observed carbon isotope ratios of TCE and its daughter products.     

Performance of a field-scale permeable reactive barrier based on organic substrate and zero-valent iron for in situ remediation of acid mine drainage

A permeable reactive barrier (PRB) was installed in Aznalcóllar (Spain) in order to rehabilitate the Agrio aquifer groundwater severely contaminated with acid mine drainage after a serious mining accident. The filling material of the PRB consisted of a mixture of calcite, vegetal compost and, locally, Fe⁰ and sewage sludge. Among the successes of the PRB are the continuous neutralisation of pH and the removal of metals from groundwater within the PRB (removals of >95 %). Among the shortcomings are the improper PRB design due to the complexity of the internal structure of the Agrio alluvial deposits (which resulted in an inefficient capture of the contaminated plume), the poor degradability of the compost used and the short residence time within the PRB (which hindered a complete sulphate reduction), the clogging of a section of the PRB and the heterogeneities of the filling material (which resulted in preferential flows within the PRB). Undoubtedly, it is only through accumulated experience at field-scale systems that the potentials and limits of the PRB technology can be determined.