分离式电解槽系统电动力学修复氟污染黏土

为解决氟污染土壤修复过程中不同形态的氟在电动力学作用下向土体中间迁移,导致修复后氟在电解槽中部累积所带来的去除率降低问题,采用自制的分离式电解槽系统,以去离子水作电解液,通过单因素实验,在0.5、1.0、1.5 V·cm-1修复电压下,对电动力学修复氟污染黏土的效果进行了研究。结果表明：分离式电解槽系统可有效修复氟污染黏土,土壤氟的去除率随着修复电压的升高而增大,最高可达61.86%;修复后各部分土壤氟含量差异较小,土壤中剩余氟没有出现累积现象;能量消耗随着修复电压的升高快速增加,而能量效率不断减小。实际应用电动力学技术修复氟污染土壤时,在考虑土壤氟去除率的同时要兼顾能量效率,以保证修复方案在经济上可行。     

电动修复技术对土壤中镉迁移的影响

以镉含量为200 mg·kg-1的模拟污染土壤为研究对象,使用电动修复技术对土壤中的镉进行去除。实验研究了不同修复电压下电流密度、电解液pH值、土壤中镉含量的变化,并重点研究了修复电压对土壤中镉迁移的影响规律。实验结果表明,通电电压越大,电场强度越强,镉的迁移量越大,电动修复效率越高,当修复电压为50 V时,阴极区域附近镉的迁移量与修复电压为5 V时相同位置镉的迁移量相比可以提高30%,实验结果为重金属污染土壤电动修复过程中镉的迁移量化研究提供了参考。     

Enhanced electrokinetic remediation of lead-contaminated soil by complexing agents and approaching anodes

Optimizing process parameters that affect the remediation time and power consumption can improve the treatment efficiency of the electrokinetic remediation as well as determine the cost of a remediation action. Lab-scale electrokinetic remediation of Pb-contaminated soils was investigated for the effect of complexant ethylenediaminetetraacetic acid (EDTA) and acetic acid and approaching anode on the removal efficiency of Pb. When EDTA was added to the catholyte, EDTA dissolved insoluble Pb in soils to form soluble Pb–EDTA complexes, increasing Pb mobility and accordingly removal efficiency. The removal efficiency was enhanced from 47.8 to 61.5 % when the EDTA concentration was increased from 0.1 to 0.2 M, showing that EDTA played an important role in remediation. And the migration rate of Pb was increased to 72.3 % when both EDTA and acetic acid were used in the catholyte. The “approaching anode electrokinetic remediation” process in the presence of both EDTA and acetic acid had a higher Pb-removal efficiency with an average efficiency of 83.8 %. The efficiency of electrokinetic remediation was closely related to Pb speciation. Exchangeable and carbonate-bounded Pb were likely the forms which could be removed. All results indicate that the approaching anode method in the presence of EDTA and acetic acid is an advisable choice for electrokinetic remediation of Pb-contaminated soil.     

酒石酸强化重金属复合污染模拟土壤电动修复过程及机理分析

为提高电动修复重金属复合污染土壤的效率,通过配制重金属复合污染模拟土壤,构建电动修复实验装置,利用2因素完全随机实验设计研究了酒石酸浓度和时间对重金属去除效果的影响;采用BCR法对土壤金属赋存形态进行了分析表征。结果表明：与对照相比,以酒石酸为电解液显著提高了重金属的去除率;重金属去除率受酒石酸浓度和修复时间影响显著;以0.05 mol·L⁻¹酒石酸为电解液修复120 h后,重金属去除效果最好,重金属总去除率为86.15%,Cu²⁺、Mn²⁺、Cd²⁺、Pb²⁺、Zn²⁺的去除率分别为75.67%、98.11%、85.1%、70.75%和90.9%。BCR分析表明,酒石酸有助于提高土壤中弱酸提取态重金属含量,提高了重金属的迁移性能,从而有利于电动修复过程。     

Cd污染土壤的电动修复及其强化

为了提高电动修复镉污染土壤的效率,通过配制镉污染土壤,搭建电动修复实验装置,研究电场强度、电解液种类和添加膨润土对电动修复镉污染土壤中总Cd去除率的影响。结果表明,电动修复时间120 h,电场强度从2.5 V·cm-1增加至3 V·cm-1时,总Cd去除率增加10.62%,电场强度从3 V·cm-1增加到3.5 V·cm-1时,去除率增加1.87%;与柠檬酸为电解液对比,乙酸的总Cd去除率增加12.14%,总耗能增加62.13%,盐酸的总Cd去除率增加18.04%,总耗能增加了187.9%;乙酸为电解液,阴阳两极电解液循环与不循环相比总Cd去除率增加25.48%,能耗增加13.69%;在靠近阴极、中部及靠近阳极土壤中添加膨润土墙,总Cd去除率分别上升20.89%、18.22%、10.67%,能耗分别降低11.00%、13.43%、13.73%。循环电解液能有效减缓电阻极化和浓差极化现象并提高总镉去除率。电动修复联合膨润土吸附,能提高土壤中的总镉去除率,同时降低能耗。     

EDTA强化电动力学修复重金属复合污染土壤

在自制的电动力学装置中,研究多种重金属复合污染土壤的电动力学修复,通过在阴极添加络合剂EDTA来提高修复效率。实验结果表明,EDTA的引入提高了修复过程中的电流值,且EDTA与重金属的络合提高了污染物向电极液的迁移效率,从而强化了电动力学修复效果。在设定的浓度(0、0.01、0.02、0.05和0.1 mol/L)中,0.1 mol/L的EDTA具有最佳的修复效率。在此实验条件下,污染土壤中的总铜、总铅和总镉的去除率分别为90.2%、68.1%和95.1%。电动力学修复后,对土壤重金属进行化学形态分析,发现电动力学修复显著改变了土壤重金属存在形态,修复后土壤中的铜、铅、镉主要以较稳定的有机态和残余态形式存在,显著降低了对周边生物和环境的毒害。     

铅污染土壤电动修复增强技术的研究

利用电动修复技术对铅污染土壤的修复进行了实验室研究,研究了修复时间和络合剂EDTA对电动修复效果的影响,分析了土壤重金属的迁移和变化特征。结果表明,在电场力作用下随着修复时间的增长污染物的去除率相应提高,去除率由修复时间5 d时的13%增加到15 d时的20%。以EDTA作为阴极控制液,EDTA可与硝酸铅反应形成溶解态的络合物,提高铅离子的移动性,从而提高修复效果。随着EDTA浓度由0.1 mol/L到0.2 mol/L,Pb的去除率由44.4%提高到61.5%,说明添加络合剂可以提高修复效果。另外,电动修复效果与铅的形态分布有密切关系,交换态和碳酸盐结合态有利于重金属铅的去除。     

表面活性剂增效电动技术修复多环芳烃污染土壤

研究了电动修复过程中修复时间和表面活性剂Triton X-100、鼠李糖脂对多环芳烃芘污染土壤的修复效果的影响。结果表明,在电动修复过程中,随着修复时间的增加,芘的去除率相应提高。通过向电解液中添加表面活性剂Triton X-100,芘的去除率从11.64%提高到了23.42%,当在电解液中添加浓度为40倍CMC的鼠李糖脂后去除率升高至36.29%,阳极附近土壤甚至达到了92.49%,这表明Triton X-100和鼠李糖脂均能促进土壤中芘的溶解和迁移,鼠李糖脂的促进作用高于Triton X-100。     

氨水循环增强电动力学技术去除土壤中的氟

为了探讨氨水增强电动力学技术修复氟污染土壤的效果及对土壤pH值的影响,在自制的电动力学装置中,1 V/cm电解电压下,以氨水作电解液,采用连续循环的方式进行研究。结果显示,氨水连续循环不仅增大了修复过程中的电流值,且使通过土壤的电流更加稳定,在提高土壤氟迁移效率的同时降低了能耗。在设定的浓度中(0、0.01、0.1和0.2 mol/L),土壤氟的去除率随着氨水浓度的升高而增加,0.2 mol/L氨水具有最大电流值26.8 mA,土壤氟的去除率也达到57.9%,氨水循环增强时两极土壤pH值差异减小。采用氨水循环增强电动力学技术,可有效修复氟污染土壤,土壤中剩余氨还可以提高土壤肥力。     

电动力耦合PRB技术修复POPs污染土壤

针对传统电动法修复土壤中持久性有机污染物（POPs）效率较低的问题,研究了电动力耦合渗透性反应墙（PRB）技术以提高污染物去除效率。以菲和2,4,6-三氯苯酚为目标污染物,铁碳混合物作为PRB填料,通过预实验确定了污染物的迁移方向及PRB的设置位置（靠近阴极）,探究最佳修复时间和电压梯度下人工配制模拟污染土壤中目标污染物的去除效果。结果表明：菲和2,4,6-三氯苯酚都是随着电渗流从阳极向阴极进行迁移。在电压梯度为1 V·cm-1,控制铁碳PRB的pH为4,铁碳质量比为6∶1的条件下,经过15 d的修复,菲总去除率可比传统电动力技术提高69.86%,2,4,6-三氯苯酚总去除率可比传统电动力技术提高71.53%。研究表明,电动力耦合PRB比传统电动力技术有明显的优势,在修复有机污染土壤方面具有良好的发展前景。     

Remediating ethylbenzene-contaminated clayey soil by a surfactant-aided electrokinetic (SAEK) process

The objectives of this research are to investigate the remediation efficiency and electrokinetic behavior of ethylbenzene-contaminated clay by a surfactant-aided electrokinetic (SAEK) process under a potential gradient of 2 Vcm(-1). Experimental results indicated that the type of processing fluids played a key role in determining the removal performance of ethylbenzene from clay in the SAEK process. A mixed surfactant system consisted of 0.5% SDS and 2.0% PANNOX 110 showed the best performance of ethylbenzene removed in the SAEK system. The removal efficiency of ethylbenzene was determined to be 63-98% in SAEK system while only 40% was achieved in an electrokinetic system with tap water as processing fluid. It was found that ethylbenzene was accumulated in the vicinity of anode in an electrokinetic system with tap water as processing fluid. However, the concentration front of ethylbenzene was shifted toward cathode in the SAEK system. The electroosmotic permeability and power consumption were 0.17 x 10(-6)-3.01 x 10(-6) cm(2)V(-1)s(-1) and 52-123 kW h m(-3), respectively. The cost, including the expense of energy and surfactants, was estimated to be 5.15-12.65 USD m(-3) for SAEK systems, which was 2.0-4.9 times greater than that in the system of electrokinetic alone (2.6 USD m(-3)). Nevertheless, by taking the remediation efficiency of ethylbenzene and the energy expenditure into account for the overall process performance evaluation, the system SAEK was still a cost-effective alternative treatment method.     

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.     

Electrokinetic remediation of a Cu contaminated red soil by conditioning catholyte pH with different enhancing chemical reagents

The effect of enhancement reagents on the efficiency of electrokinetic remediation of Cu contaminated red soil is evaluated. The enhancement agents were a mix of organic acids, including lactic acid+NaOH, HAc-NaAc and HAc-NaAc+EDTA. The soil was prepared to an initial Cu concentration of 438 mgkg(-1) by incubating the soil with CuSO4 solution in a flooded condition for 1 month. Sequential extraction showed that Cu was partitioned in the soil as follows: 195 mgkg(-1) as water soluble and exchangeable, 71 mgkg(-1) as carbonate bound and 105 mgkg(-1) as Fe and Mn oxides. The results indicate that neutralizing the catholyte pH maintains a lower soil pH compared to that without electrokinetic treatment. The electric currents varied depending upon the conditioning solutions and increased with an increasing applied voltage potential. The electroosmotic flow rate changed significantly when different conditioning enhancing reagents were used. It was observed that lactic acid+NaOH treatments resulted in higher soil electric conductivities than HAc-NaAc and HAc-NaAc+EDTA treatments. Ultimately, enhancement by lactic acid+NaOH resulted in highest removal efficiency (81% Cu removal) from the red soil. The presence of EDTA did not enhance Cu removal efficiencies from the red soil, because EDTA complexed with Cu to form negatively charge complexes, which slowly migrated toward the anode chamber retarding Cu2+ transport towards the cathode.     

几种典型土壤对电动修复镉污染效果的影响

选择5种典型土壤进行了镉污染的电动修复研究。结果表明,经12 d电动修复后,黑土、潮土、红壤、水稻土和黄棕壤中镉的去除率依次为16.7%、21.0%、47.1%、10.7%和12.6%。红壤靠阳极附近Cd含量由初期435 mg·kg-1降至32.4 mg·kg-1,迁移率高达92.5%。黑土、红壤和潮土都维持了较高的电流强度和电渗流量,但由于红壤对碱的缓冲能力较强,修复效果最好。水稻土中电渗流量高,但由于电流低,镉的去除率不高,说明电动修复中电迁移作用强于电渗析。修复后,土壤中可交换态镉、碳酸盐结合态镉、铁锰氧化物结合态镉总量减少,残渣态镉总量增加,有机结合态在阳极附近总量减少、阴极附近总量增加。上述结论揭示了电动修复的土壤镉污染的主要机制,通过镉的运动轨迹和形态分布,可预测不同土壤的电动修复效果,同时能改变不同土壤的电动修复策略,为场地修复提供参考。     

电动与渗透反应格栅联合修复镉污染地下水实验

通过实验方法研究了地下水中镉污染的电动力学修复效果,并分析其迁移变化特征。实验结果表明,电动修复中由于阴阳两极的氧化还原反应造成电极附近pH值产生明显变化,其中阳极附近的pH值由开始时的7.0逐渐变小到6.8,而阴极附近则相反,由开始时6.9逐渐增大到9.1,表明土壤的酸碱条件变化明显。Cd浓度变化反映在自然渗透条件下含水层中重金属污染物的迁移能力较弱,阳极附近地下水中Cd的去除率仅8.4%,而在电场作用下地下水中重金属的浓度发生明显变化,使得重金属污染物能在电极附近富集而被去除,当实验电场强度为0.5 V/cm时,Cd在阴极的累积使得阳极附近地下水中去除率为72.9%,说明电动修复重金属Cd污染地下水的效果明显好于自然渗透状态。     

铬污染土壤电动修复过程中典型阴离子的迁移特征

为揭示典型阴离子在电动修复六价铬污染土壤过程中的迁移行为,以人工配置的Cr (Ⅵ)污染蒙脱石模拟供试土壤,蒸馏水作为阴阳极电解液,在电压梯度为2 V·cm⁻¹的条件下进行电动修复实验;并分别对比分析各组实验的电流、pH、电导率、能量损耗参数的变化。结果表明,5种阴离子在土壤电动修复过程中的迁移顺序为：${{\rm{NO}}_3^ - \gt {\rm{Cr}}\left( {{\text{Ⅵ}}} \right) \approx {\rm{C}}{{\rm{l}}^ - } \gt {\rm{SO}}_4^{2 - } \gg {\rm{PO}}_4^{3-}}$。相比于酸性土壤,偏中性的土壤环境更利于Cr(Ⅵ)向阳极的迁移,而酸性土壤会导致电动修复过程能耗的增加,更容易产生聚焦现象。土壤中${{\rm{CO}}_3^{2 - }}$、OH⁻和${{\rm{PO}}_4^{3 - }}$的存在,能有效地缓解电动修复过程中产生的聚焦现象,而且能加速土壤中Cr(Ⅵ)的去除;${{\rm{PO}}_4^{3 - }}$的存在能将Cr(Ⅵ)的去除率提高到99.9%以上。本研究结果可为电动修复六价铬污染土壤电解液的选择提供参考。     

Simultaneous removal of organic compounds and heavy metals from soils by electrokinetic remediation with a modified cyclodextrin

Thousands of sites are contaminated with both heavy metals and organic compounds and these sites pose a major threat to public health and the environment. Previous studies have shown that electrokinetic remediation has potential to remove heavy metals and organic compounds when they exist individually in low permeability soils. This paper presents the feasibility of using cyclodextrins in electrokinetic remediation for the simultaneous removal of heavy metals and polycyclic aromatic hydrocarbons (PAHs) from low permeability soils. Kaolin was selected as a model low permeability soil and it was spiked with phenanthrene as well as nickel at concentrations of 500 mg kg-1 each to simulate typical mixed field contamination. Bench-scale electrokinetic experiments were conducted using hydroxypropyl beta-cyclodextrin (HPCD) at low (1%) and high (10%) concentrations and using deionized water in control test. A periodic voltage gradient of 2VDC cm-1 (with 5 d on and 2 d off) was applied to all the tests, and 0.01 M NaOH was added during the experiments to maintain neutral pH conditions at anode. In all tests, nickel migrated as Ni2+ ions towards the cathode and most of it was precipitated as Ni(OH)2 within the soil close to the cathode due to high pH condition generated by electrolysis reaction. The solubility of phenanthrene in the flushing solution and the amount of electroosmotic flow controlled the migration and removal of phenanthrene in all the tests. Even though high flow was generated in tests using deionized water and 1% HPCD, migration and removal of phenanthrene was low due to low solubility of phenanthrene in these solutions. The test with 10% HPCD solution showed higher solubility of phenanthrene which caused it migrate towards the cathode, but further migration and removal was retarded due to reduced electric current and electroosmotic flow. Approximately one pore volume of flushing resulted in approximately 50% removal of phenanthrene from the soil near the anode. Sustained higher electroosmotic flow with higher concentration cyclodextrin and maintaining low soil pH near cathode should be investigated to increase removal efficiency of both phenanthrene and nickel.     

电动增强技术修复镉污染土壤及其修复机理

选择小分子有机酸——酒石酸、草酸作为增强试剂,研究在不同浓度小分子有机酸作用下,电动修复土壤重金属镉Cd（Ⅱ）的迁移和去除机制。实验中以胡敏素为吸附剂并将其以包裹的形式添加在在电动装置中,以乙酸-乙酸钠为电解液,同时在两极室之间循环电解液以控制土壤pH值变化。结果表明,电动修复技术促进了重金属的去除。小分子有机酸的加入使弱酸提取态的重金属镉Cd（Ⅱ）的去除率大大提高,可达67.07%。不同浓度的小分子有机酸对电动修复的促进效果不同,随着浓度的持续增加,电动修复效果降低。     

土壤中铬电动修复过程及影响因素

实验筛选出阳极pH、阴极pH、电压梯度、电极形状4种影响因素,以黏土为研究对象,设计正交实验和对比实验研究铬的电动修复过程。结果表明,最重要的影响因素为电压梯度,其他影响因素重要性排序为阳极pH、阴极pH、电极形状;在电压梯度为1.5 V·cm-1下,以去离子水作为电解质,分别控制阴极和阳极pH在11和3,取得很好的去除效果,144 h后铬迁移率达到80.9%。总铬和六价铬分布规律类似,从阳极到阴极呈现逐渐下降的趋势。经过电动修复后土壤中水溶态铬比例减少,可氧化态和残渣态比例增大。铬电动修复控制系统在微电流范围内可取得很好的去除效果。     

介质阻挡放电与脉冲电晕放电修复芘污染土壤的对比研究

选取芘作为多环芳烃的代表污染物,利用介质阻挡及脉冲电晕2种放电方式产生的低温等离子体对芘污染的土壤进行修复。通过污染物处理率、影响因素和能量利用效率等实验计算结果对2种放电方式下土壤的修复效果进行比较,并从放电方式的原理、特点和反应器结构等角度进行分析。结果表明：在芘初始浓度为100 mg·kg-1、电极间隙为14 mm时,介质阻挡放电对土壤中芘的处理率较高,可达60.6%,经GC-MS图谱检测分析,其多数产物分子量小、结构简单,但该放电方式受电气参数影响较大,当电极间隙增大到20 mm时,处理率则低至28.3%,其最高能量效率仅为0.321 mg·kJ-1;而脉冲电晕放电在不同条件下处理效果稳定,电极间隙为14~20 mm时,处理率均能达50%左右,且在不同实验条件下,其能量效率为2.29~3.76 mg·kJ-1,是介质阻挡放电的10余倍。脉冲电晕放电方式在处理比污染土壤时要优于介质阻挡放电。