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1.
Liang C  Bruell CJ  Marley MC  Sperry KL 《Chemosphere》2004,55(9):1213-1223
The objective of the laboratory study is to examine the conditions under which transition metal ions (e.g., ferrous ion, Fe2+) could activate the persulfate anion (S2O8(2)-) to produce a powerful oxidant known as the sulfate free radical (SO4-*) with a standard redox potential of 2.6 V. The SO4-* is capable of destroying groundwater contaminants in situ such as trichloroethylene (TCE). Experiments using Fe2+ as an activator under various molar ratios of S2O8(2)-/Fe2+/TCE in an aqueous system indicated that partial TCE degradation occurred almost instantaneously and then the reaction stalled. Either destruction of SO4-* in the presence of excess Fe2+ or the rapid conversion of all Fe2+ to Fe3+ limited the ultimate oxidizing capability of the system. Sequential addition of Fe2+ in small increments resulted in an increased TCE removal efficiency. Therefore, it appeared that Fe2+ played an important role in generating SO4-*. An observation of oxidation-reduction potential (ORP) variations revealed that the addition of sodium thiosulfate (Na2S2O3) to the ferrous ion activated persulfate system could significantly decrease the strong oxidizing conditions. It was hypothesized that the thiosulfate induced reducing conditions might convert Fe3+ to a lower valence state of Fe2+, making the Fe2+ available to activate persulfate decomposition. The sequential addition of thiosulfate (S2O3(2)-), after the initial stalling of ferrous ion activated persulfate oxidation of TCE, resulted in an improvement in TCE removal. The ferrous ion activated persulfate-thiosulfate redox couple resulted in fairly complete TCE degradation in aqueous systems in a short time frame. In soil slurry systems, TCE degradation was slower in comparison to aqueous systems.  相似文献   

2.
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.  相似文献   

3.
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.  相似文献   

4.
原位化学氧化法在土壤和地下水修复中的研究进展   总被引:1,自引:0,他引:1  
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  相似文献   

5.
氧化亚铁硫杆菌对亚铁离子的氧化及其动力学研究   总被引:6,自引:0,他引:6  
采用9K培养基研究了氧化亚铁硫杆菌氧化Fe^2+过程中,pH和氧化还原电位的变化规律,并对Fe^2+的氧化过程进行动力学分析,确定了其反应级数及反应速率常数。结果表明,(1)在温度为30℃,摇床转速为150r/min的条件下,氧化亚铁硫杆菌的最佳接种量为10.0%;(2)Fe^2+初始质量浓度在11.39~21.72g/L时,随着浓度的增大,Fe^2+达到100%转化率需要的时间增加;(3)氧化亚铁硫杆菌对Fe^2+的氧化可近似看作一级反应,反应速率常数为0.0527~0.0788h。  相似文献   

6.
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.  相似文献   

7.
以亚铁离子活化过硫酸氢钾(PMS)所产生的硫酸根自由基为氧化剂,氧化水中的酮洛芬,考察了pH值、温度、Fe2+浓度、Fe2+/PMS摩尔比以及Fe2+投加方式等因素对酮洛芬氧化降解的影响,探究氧化降解酮洛芬(KTP)的最佳运行条件。结果表明,在实验范围内,pH值为3、温度为45℃和Fe2+/PMS/KTP浓度比为20/15/1时酮洛芬的降解效果最好,酮洛芬的去除率达到66.8%。分批式投加Fe2+,使硫酸根自由基(SO4·-)持续生成,这样更有利于酮洛芬的降解。  相似文献   

8.
通过亚铁离子活化过硫酸氢钾复合盐产生氧化性的硫酸根自由基,以吲哚美辛(IM)为目标污染物,研究了不同亚铁离子浓度和过硫酸氢钾浓度,以及加入Cl-离子和腐殖酸对吲哚美辛降解情况的影响。结果表明,[IM]:[PMS]:[Fe2+]=1:2:2条件下,IM的去除率接近100%;低浓度的Cl-抑制吲哚美辛的降解,高浓度则为促进作用;而腐殖酸都在不同程度上抑制了吲哚美辛的降解。经淬灭实验表明,亚铁离子活化过硫酸氢钾降解吲哚美辛中起主要作用的自由基是SO4-·。该方法能在短时间内高效降解吲哚美辛,为实际废水中吲哚美辛去除提供参考。  相似文献   

9.
在不同pH值、Fe2+浓度和过硫酸氢钾复合盐(PMS)浓度下,探究降解萘普生(NPX)的最佳条件,并通过分批投加Fe2+和改变投加顺序的方式,提高降解NPX的效率.结果表明,NPX在pH=3的条件下,降解效果最好;Fe2+浓度改变时,PMS/ Fe2+/NPX=1/0.75/1条件下,NPX去除率最高;分批投加Fe2+和先投加Fe2+均可大幅提高NPX去除率.缓慢少量的产生硫酸根自由基(SO4·-)更利于处理有机物,Fe2+的浓度则在产生自由基方面起着重要作用.  相似文献   

10.
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.  相似文献   

11.
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.  相似文献   

12.
在模拟原沉积物弱碱性及含水率的条件下,分别研究了2种高级氧化反应体系:H2O2辅助加入催化剂FeSO4或Fe2(SO4)3及Na2S2O8辅助加入催化剂FeSO4或CaO及热催化对污染滩涂沉积物中石油烃的去除效果及其影响因素。同时,还模拟研究了长江口潮汐作用对滩涂石油污染修复效果的影响。研究表明:H2O2与样品的质量投加比为0.05,FeSO4和Fe2(SO4)3与H2O2摩尔投加比均为0.1时,石油烃去除率分别达到48.9%和57.4%;Na2S2O8本身氧化能力较强,单一Na2S2O8与样品的质量比大于0.01时,石油烃去除率达到46%以上;而在Na2S2O8最佳投加比条件下,FeSO4、CaO与Na2S2O8摩尔比为0.05和0.9时,去除率分别达到60.4%和51.3%以上,同时最佳催化温度为50 ℃。潮汐作用对芬顿试剂氧化修复滩涂石油污染具有促进作用,而高浓度污染滩涂区域建议采用阻隔修复。  相似文献   

13.
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。  相似文献   

14.
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.  相似文献   

15.
主要探究泥浆系统中Fe2+活化过碳酸钠(SPC)降解三氯乙烯(TCE)的效果。通过批次实验研究土壤对TCE的吸附作用,并考察泥浆系统中SPC和Fe2+投加量对TCE去除效果的影响。结果表明,土壤对TCE具有一定的吸附作用;泥浆系统中,土壤含有的有机质越多,TCE去除效果越低;当SPC/TCE摩尔比为5/1~20/1时,SPC投加量对TCE去除影响不明显,TCE去除效果随Fe2+投加量增大而提高。当水土质量比为30/1,TCE初始浓度为20 mg/L时,SPC/Fe2+/TCE最优摩尔比为10/30/1,此时TCE最终去除率达到97.5%。综上所述,Fe2+活化过碳酸钠降解三氯乙烯快速高效,为应用于实际场地修复提供有效的理论依据。  相似文献   

16.
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.  相似文献   

17.
重质非水相液体(DNAPLs)是土壤及地下水中广泛存在的有机污染物,原位热处理技术是目前修复受DNAPLs污染土壤及地下水的最具潜力的技术之一。综述了国内外常用原位热处理技术的基本原理及其影响因素,介绍了相关现场应用实例,并展望了该技术未来的应用前景和发展趋势,以期为中国污染土壤及地下水的原位修复提供有益借鉴。  相似文献   

18.
Mathematical models were developed to investigate the characteristics of gaseous ozone transport under various soil conditions and the feasibility of in situ ozone venting for the remediation of unsaturated soils contaminated with phenanthrene. On the basis of assumptions for the mass transfer and reactions of ozone, three approaches were considered: equilibrium, kinetic, and lump models. Water-saturation-dependent reactions of gaseous ozone with soil organic matter (SOM) and phenanthrene were employed. The models were solved numerically by using the finite-difference method, and the model parameters were determined by using the experimental data of Hsu [The use of gaseous ozone to remediate the organic contaminants in the unsaturated soils, PhD Thesis, Michigan State Univ., East Lansing, MI, 1995]. The transport of gas-phase ozone is significantly retarded by ozone consumption due to reactions with SOM and phenanthrene, in addition to dissolution. An operation time of 156 h was required to completely remove phenanthrene in a 5-m natural soil column. In actual situations, however, the operation time is likely to be longer than the ideal time because of unknown factors including heterogeneity of the porous medium and the distribution of SOM and contaminant. The ozone transport front length was found to be very limited (< 1 m). The sensitivity analysis indicated that SOM is the single most important factor affecting in situ ozonation for the remediation of unsaturated soil contaminated with phenanthrene. Models were found to be insensitive to the reaction mechanisms of phenathrene with either gas-phase ozone or dissolved ozone. More study is required to quantify the effect of OH* formation on the removal of contaminant and on ozone transport in the subsurface.  相似文献   

19.
Liang C  Lee IL  Hsu IY  Liang CP  Lin YL 《Chemosphere》2008,70(3):426-435
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.  相似文献   

20.
印制线路板生产过程中会排放各类废水,其中的综合废水中含有络合铜化合物。目前针对络合铜的去除,硫化钠法和亚铁法的研究较为成熟。然而,现有的研究主要针对于某一方法的优化,并没有从工程应用的角度对2种方法进行一个全面的经济技术比较。针对含络合铜废水,在优化了硫化钠法和亚铁法的操作条件的基础上,结合药剂成本和产生污泥的处理成本,从经济和技术角度对比了2种方法。结果表明,硫化钠法药剂费和污泥处理费成本为2.25元·t-1,低于亚铁法的2.68元·t-1,而基建费用和运行风险则高于亚铁法。  相似文献   

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