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。     

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%,Cu~(2+)、Mn~(2+)、Cd~(2+)、Pb~(2+)、Zn~(2+)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。     

重金属污染土壤的草酸和EDTA混合淋洗研究

采用不同浓度的草酸(oxalic acid,OX)和乙二胺四乙酸(EDTA)混合的淋洗方法研究重金属污染土壤的最佳混合淋洗方式,探讨了液固比、淋洗时间及pH对淋洗效果的影响,并分析了0.2 mol/L OX+0.2 mol/L EDTA处理前后土壤中重金属形态的变化。结果表明,采用0.2 mol/L OX+0.2 mol/L EDTA混合的淋洗法可同时去除多种重金属,且对Cu、Zn、Ni和Cr的去除率明显高于单用OX和EDTA,去除率分别为Cu 41.29%、Zn 84.73%、Ni 54.2%和Cr 66.01%。0.2mol/L OX+0.2 mol/L EDTA在液固比为5∶1、淋洗时间为4 h、pH为6时可分别达到最佳淋洗效果,且分别为Cu 62.59%、Zn 93.48%、Ni 55.95%和Cr 71.57%;Cu 50.47%、Zn 86.67%、Ni 61.53%和Cr 72.68%;Cu 44.40%、Zn 81.82%、Ni68.76%和Cr 74.93%。形态分析结果表明,0.2 mol/L OX+0.2 mol/L EDTA能较好地改变土壤中重金属形态的分布。     

超声强化淋洗修复Pb、Cd、Cu复合污染土壤

针对传统淋洗法修复土壤中重金属效率较低的问题,研究了超声强化淋洗技术以提高重金属去除率。以铅(Pb)、镉(Cd)、铜(Cu)为目标污染物,在0.05 mol·L~(-1)柠檬酸、0.05 mol·L~(-1)EDTA和0.05 mol·L~(-1)皂角苷作为淋洗剂条件下,使用传统振荡、超声强化以及超声波加振荡3种不同的作用方式,对Pb、Cd、Cu的去除率进行比较,并对3种不同淋洗方式后Pb、Cd、Cu的形态变化进行了探讨。结果表明,当使用柠檬酸和皂角苷作为淋洗剂进行振荡淋洗时,重金属洗脱效果不理想。超声对于强化柠檬酸洗脱效果并不明显,而对于强化皂角苷洗脱重金属效果明显,平均去除率提高了120.47%。当淋洗剂为EDTA时,土壤样品在传统振荡2 h作用下,对Pb、Cd、Cu的去除率依次为50.33%、76.65%和47.35%,而在超声波30 min条件下对Pb、Cd、Cu的去除率依次为82.19%、83.31%和53.89%,平均去除率高出28.60%,可显著提高重金属去除率,缩短淋洗时间。但超声波30 min加传统振荡2 h相较于单纯超声强化效果提升不明显。通过对比3种淋洗方式后土壤中的Pb、Cd、Cu形态发现,酸可提取态的重金属在超声强化作用后有明显降低,同时超声强化对于铁锰氧化物结合态、有机物结合态和残渣态也具有较好的去除能力。因此,超声强化在化学淋洗中的应用具有一定的可行性,是一种简单、极快速去除污染场地中重金属Pb、Cd、Cu的增效手段。     

铅锌厂重金属污染土壤的螯合剂淋洗修复及其应用

为探讨螯合剂淋洗法在修复铅锌厂周边重金属污染土壤的修复效果及淋洗后土壤利用价值,研究采用振荡淋洗的方法比较了乙二胺四乙酸(EDTA)、次氮基三乙酸三钠盐(NTA)、[S,S]-乙二胺-N,N-二琥珀酸三钠盐(EDDS)乙二醇-双-(2-氨基乙醚)四乙酸(EGTA)4种螯合剂对不同污染程度土壤中Cd、Cu、Zn、Pb的去除效果,并用BCR连续提取法分析了淋洗前后土壤重金属形态的变化,最后通过黑麦草盆栽实验及土壤酶分析,探讨了土壤经淋洗后的利用价值。结果表明,4种螯合剂中EDTA对Cd、Cu、Zn和Pb的去除率比其他螯合剂的去除率高,其中对高污染土壤4种重金属离子的去除率最大,分别为Cd 90.98%、Cu 42.10%、Zn 56.98%和Pb 52.03%,4种重金属中Cd的去除效果分别为EDTANTAEDDSEGTA;EDTA能有效去除酸溶态、可还原态土壤重金属,而对可氧化态和残余态土壤重金属作用效果不明显;EDTA淋洗土种植黑麦草后土壤脱氢酶、碱性磷酸酶和β-葡糖苷酶活性均高于NTA淋洗后土壤中酶活性。综合考虑淋洗效率、淋洗剂的成本和利用价值等因素,可以认为,采用EDTA和NTA淋洗修复重金属污染土壤具有一定的实用性,并以EDTA效果较佳。     

不同增强剂的电动技术对土壤中镉去除及土壤酶活性的影响

为了探讨基于不同增强剂的电动技术对重金属污染土壤的修复效果,采用0.1%浓度的草酸、柠檬酸、已二胺四乙酸(EDTA)、甲基甘氨酸二乙酸(MGDA)作为阴极电解液,电压梯度3 V·cm~(-1)连续通电10 d,同时考查土壤中Cd的电迁移效果以及土壤酶(脲酶、酸性磷酸酶、过氧化氢酶)活性的变化。结果表明:相对于传统电动法(清水组),增强剂明显提高了Cd在土壤中的迁移效果,且人工螯合剂效果优于有机酸,对总Cd去除率为MGDA(63.08%)EDTA(23.75%)柠檬酸(18.43%)草酸(16.41%)清水(8.73%)。相比于清水组,EDTA抑制了土壤中3种酶活性,柠檬酸、草酸可以改善脲酶和过氧化氢酶的活性,MGDA显著提高了3种酶的活性。结合Cd去除率和酶的影响分析,MGDA不仅能显著提高电动修复效率,且具备较低的土壤环境风险。     

柠檬酸强化电动去除和回收污泥中的重金属

探讨了柠檬酸对污泥中重金属形态的影响,并以柠檬酸为络合剂、以杭州七格污水处理厂城市污泥为研究对象,在0.8 m A·cm-2恒定电流密度条件下运行120 h,在5组柠檬酸浓度分别为0.00、0.05、0.10、0.20和0.30 mol·L~(-1)的条件下,采用自行设计的双层双阳极反应器对污泥中重金属进行电动去除和回收实验。结果显示,柠檬酸能促使污泥中大量的Zn由可还原态转化为酸可提取态,但对Cu的形态影响不大。电动处理实验中,添加柠檬酸后Zn和Cu的去除率都有明显提高,当柠檬酸浓度为0.20 mol·L~(-1)时,Zn的去除率最大达58.3%,Cu的去除率为42.4%;当柠檬酸浓度为0.10 mol·L~(-1)时,Cu的去除率最大为51.7%,Zn的去除率为46.4%。柠檬酸的最佳添加浓度为0.10~0.20 mol·L~(-1),当柠檬酸添加量超过0.20 mol·L~(-1),Zn和Cu的去除率反而会因为络合物在阳极区的沉淀而降低。     

EDTA/纳米羟基磷灰石联合修复重金属污染土壤

土壤淋洗可能导致残留重金属活化,采用淋洗/钝化联合修复重金属污染土壤可在一定程度上减少这一影响。研究了EDTA淋洗、纳米羟基磷灰石钝化及两者联合修复对土壤重金属洗脱率、TCLP浸出浓度、化学形态分布的影响,构建了涵盖土壤重金属残留量、生物有效性和生理毒性的环境风险评价方法,对淋洗、钝化及其联合修复进行了评价。结果发现,EDTA淋洗对Pb和Cu的洗脱效果较好,对Zn浸出浓度的削减率较高。当EDTA投加量为2 g·L~(-1)时,Zn的浸出浓度降低了70.40%。纳米羟基磷灰石对Pb和Zn具有较好的钝化效果,对Cu和Cd的钝化作用相对较弱。当纳米羟基磷灰石投加量为2%时,Pb浸出浓度削减率高达89.65%。淋洗/钝化联合修复大幅度降低了Pb和Cd的浸出浓度,降低了可还原态Cu残留量、可还原态和残渣态Cd残留量,以及弱酸提取态和可还原态Zn、Pb残留量。当EDTA和纳米羟基磷灰石投加量分别为1 g·L~(-1)和1%时,土壤重金属总环境风险削减率达到74.12%。EDTA对土壤中Cu和Cd的洗脱效果较好,后续钝化修复作用有限,Pb和Zn则可通过淋洗/钝化联合修复大幅度提高削减环境风险削减率。     

乳酸发酵液淋洗铅锌矿尾矿坝口底泥中的重金属铅

为了降低尾矿中重金属对环境造成的危害,利用乳酸发酵液对铅尾矿坝口底泥进行了淋洗研究,从而探析低分子质量有机酸在土壤重金属淋洗修复中的应用前景。结果表明:乳酸对底泥中的Pb具有较好的去除率,当选择发酵菌种为米根霉,发酵时间为48 h,米根霉发酵生产的乳酸含量可达到14%;该发酵液对Pb的去除率达到了19.52%,与同一酸度纯乳酸淋洗铅的去除率仅差2.6%。从铅的形态分析可知,乳酸发酵液对尾矿坝口底泥中酸可提取态铅和可氧化态铅的去除率分别为80%和50%。利用发酵生产有机酸淋洗修复土壤中的重金属具有很好的潜力。     

功能微生物对污染农田土壤中铅锌的溶出实验

用微生物修复重金属污染的土壤是当今的研究热点之一。试图寻找一类可以增加土壤中重金属铅、锌的可溶态的功能微生物,并研究该微生物在不同土壤含水率和不同投菌比条件下对铅、锌溶出作用的影响。最终筛选出符合条件的菌JK3,并发现当土壤含水率为35%,投菌比为0.15 mL/g土(菌液OD=1)时,土壤中铅和锌的可溶态增加量最多。其中,可溶态铅的含量由原来的0.49 mg/kg增加到了5.04 mg/kg,可溶态锌的含量由原来的2.23 mg/kg增加到了22.44mg/kg。该方法为后续用植物提取或化学淋洗等方法将土壤中的重金属彻底去除提供了可能。     

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.     

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.     

可渗透反应复合电极法对土壤重金属的电动去除

将零价铁(Fe0)、沸石等活性材料附着在电极上形成可渗透反应层并构成可渗透反应复合电极,采用不同的复合电极对Cd2+、Ni 2+、Pb2+和Cu2+等4种阳离子型重金属污染土壤进行了电动力学修复。研究了不同可渗透反应复合电极对土壤pH的控制效果以及对重金属的去除作用,分析了迁移到复合电极中的重金属形态变化。结果表明,复合电极中添加酸、碱性沸石并适时更换,可有效中和、截留阴阳极电解产生的OH-和H+,避免或减缓土壤酸碱迁移带的形成,防止重金属离子的过早沉淀及土壤过度酸化,极大提高了重金属的去除率。复合电极中Fe0可将迁移进来的重金属离子进行还原稳定,实现重金属污染物的捕获与固定,与迁移到沸石复合电极中的4种重金属不稳定态相比,"Fe0+沸石"复合电极中重金属不稳定态分别下降了61.4、60.5、61.4、57.1百分点。结果还显示,阴极采用"Fe0+沸石"复合电极并适时进行更换,施加1.5V/cm的直流电压修复10d后,土壤中Cd、Ni、Pb、Cu的总去除率分别为44.5%、41.5%、33.5%和36.7%,且进一步延长修复时间和持续更换电极可获得更为理想的修复效果。     

EDTA and HCl leaching of calcareous and acidic soils polluted with potentially toxic metals: remediation efficiency and soil impact

The environmental risk of potentially toxic metals (PTMs) in soil can be diminished by their removal. Among the available remediation techniques, soil leaching with various solutions is one of the most effective but data about the impact on soil chemical and biological properties are still scarce. We studied the effect of two common leaching agents, hydrochloric acid (HCl) and a chelating agent (EDTA) on Pb, Zn, Cd removal and accessibility and on physico-chemical and biological properties in one calcareous, pH neutral soil and one non-calcareous acidic soil. EDTA was a more efficient leachant compared to HCl: up to 133-times lower chelant concentration was needed for the same percentage (35%) of Pb removal. EDTA and HCl concentrations with similar PTM removal efficiency decreased PTM accessibility in both soils but had different impacts on soil properties. As expected, HCl significantly dissolved carbonates from calcareous soil, while EDTA leaching increased the pH of the acidic soil. Enzyme activity assays showed that leaching with HCl had a distinctly negative impact on soil microbial and enzyme activity, while leaching with EDTA had less impact. Our results emphasize the importance of considering the ecological impact of remediation processes on soil in addition to the capacity for PTM removal.     

Fe~Ⅱ（EDTA）协同生物转鼓过滤器去除NO的实验研究

采用自行研制的生物转鼓反应器（RDB）处理难溶于水的NO废气,为提高NO的传质系数和去除效率,实验考察了营养液中添加FeⅡ（EDTA）络合剂协同RDB以提高NO去除效率的过程。结果表明,当空床停留时间（EBRT）为0.96 min时,在营养液中添加FeⅡ（EDTA）至100 mg/L后,NO的去除效率从70.78%升至79.26%。未添加FeⅡ（EDTA）时NO去除率随营养液的增加下降,添加FeⅡ（EDTA）至100 mg/L后,去除率随营养液量的增加先上升后下降,且下降速率比上升速率大。随着营养液中FeⅡ（EDTA）浓度从0增加至500 mg/L,实验最佳温度从32.5℃升至47.5℃,但添加FeⅡ（ED-TA）至100 mg/L对实验的最适pH值没有太大影响。     

Multi-step leaching of Pb and Zn contaminated soils with EDTA

The efficiency of multi-step leaching of heavy metal contaminated soils was evaluated in a laboratory scale study. Four different soils contaminated with Pb (1136+/-16-4424+/-313mgkg(-1)) and Zn (288+/-5-5489+/-471mgkg(-1)) were obtained from industrial sites in the Mezica Valley, Slovenia and Príbram district, Czech Republic. Different dosages (2.5-40mmolkg(-1)) of ethylenediamine tetraacetate (EDTA) were used to treat soils in 1-10 leaching steps. Higher EDTA dosages did not result in a proportional gain in Pb and Zn removal. EDTA extracted Pb more efficiently than Zn from three of four tested soils. The percentage of removed Zn did not exceed 75% regardless of the soil, EDTA dosage and leaching steps. Significantly more Pb (in three of four soils) and Zn were removed from soils when the same amount of EDTA was applied in several leaching steps. The interference of major soil cations Fe and Ca with EDTA complexation as a possible factor affecting Pb and Zn removal efficiency with multi-step heap leaching was examined and is discussed. The results of our study indicate that, for some soils, using multi-step leaching instead of the more traditionally used single dose EDTA treatment could improve heavy metal removal efficiency and thus the economics of soil remediation.     

Electrokinetic enhancement removal of heavy metals from industrial wastewater sludge

An enhanced electrokinetic process for removal of metals (Cr, Cu, Fe, Ni, Pb, Zn) from an industrial wastewater sludge was performed. The electrokinetic experiments were conducted under a constant potential gradient (1.25 V cm(-1)) with processing fluids of tap water (TW), sodium dodecylsulfate (SDS) and citric acid (CA) for 5 days. Results showed that metal removal efficiency of heavy metals for EK-TW, EK-SDS and EK-CA systems are 11.2-60.0%, 37.2-76.5%, and 43.4-78.0%, respectively. A highest metal removal performance was found in EK-CA system. The removal priority of investigated metals from sludge by EK process was found as: Cu > Pb > Ni > Fe > Zn > Cr. The results of sequential extraction analysis revealed that the binding forms of heavy metals with sludge after electrokinetic process were highly depend upon the processing fluid operated. It was found that the binding forms of metals with sludge were changed from the more difficult extraction type (residual and sulfate fractions) to easier extraction types (exchangeable, sorbed, and organic fraction) after treatment by electrokinetic process. Results imply that if a proper treatment technology is followed by this EK process to remove metals more effectively, this treated sludge will be more beneficial for sludge utilization afterwards. Before it was reused, the risk associated with metals of more mobile forms to the environment need to be further investigated. The cost analysis was also evaluated for the investigated electrokinetic systems.     

微波修复氯丹污染土壤中氯丹降解的影响因素研究

对微波修复氯丹污染土壤进行研究,重点考察了含水率、微波辐射时间、碱浓度、活性炭添加量和土壤量对其中氯丹降解的影响。结果表明:(1)总体上,氯丹降解率随着含水率的增加而先增加后减少,随着微波辐射时间的延长而增加。当含水率为20%、微波辐射15min后,α-氯丹和γ-氯丹的降解率分别增加到65%和56%。(2)总体上,氯丹降解率随着微波辐射时间的延长而不断增加,7min后氯丹的降解过程基本趋于平衡。10mol/L氢氧化钠溶液存在条件下氯丹降解效果最好,15min时α-氯丹和γ-氯丹的降解率分别为94%和82%。(3)氢氧化钠溶液最佳摩尔浓度为10mol/L。(4)添加1.0g活性炭条件下,氯丹降解率随着微波辐射时间延长而迅速增加,15min时α-氯丹和γ-氯丹的降解率分别为98%和94%。(5)当土壤和活性炭的质量比固定为15∶1时,随着土壤量的增加,氯丹降解率明显增加。     

Removal of fluorine from contaminated soil by electrokinetic treatment driven by solar energy

Instead of direct current power supply, a series of electrokinetic remediation experiments driven by solar energy on fluorine-contaminated soil were conducted in a self-made electrolyzer, in order to reduce energy expenditure of electrokinetic remediation. After the 12-day electrokinetic remediation driven by solar energy, the removal efficiency of fluorine was 22.3 %, and electrokinetic treatment had an impact on changes in partitioning of fluorine in soil. It proved that the combination of electrokinetics and solar energy was feasible and effective to some extent for the remediation of fluorine-contaminated soil. Meanwhile, the experimental results also indicated that the electromigration was a more dominant transport mechanism for the removal of fluorine from contaminated soil than electroosmosis, and the weather condition was the important factor in affecting the removal efficiency.