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.     

镉污染胶东棕壤的电动力学修复研究

在Cd污染的胶东棕壤土体两端加以1 V/cm的直流电压梯度进行电动力学修复.考察了电动力学修复过程中阴阳极电解液pH、电渗流量和电流密度的变化,并将处理后的土体分6段进行了分析,主要参数为pH、电导率、土壤中Cd的浓度及其形态分析.结果表明,经过445.0 h的电动力学修复,阳极附近3段土壤中Cd的去除率分别达到98.19%、97.01%和96.24%;阴极附近3段土壤中出现了Cd富集现象,且pH为5.88的土壤段Cd的富集率最高.     

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。     

电动联合法对复合重金属污染底泥的修复

河流与湖泊底泥中重金属污染物的清除是实现水体彻底净化及底泥工程利用的关键。以增加了电解液循环的电动联合装置为修复设备,以Cu、Zn、Pb、Cr、Ni污染底泥为研究对象,结合小试模拟和中试模拟实验,明确修复装置对复合污染底泥的净化修复效果,并优化污染物回收的技术参数。结果表明,增设电解液循环有助于增强复合污染底泥中重金属离子的迁出,在小试模拟和中试模型实验中,底泥污染物的去除率分别达到了74%~84%和52%~60%;中试模型实验修复后底泥中的Cr、Cu、Ni和Zn含量分别为140.31、314.47、250.93、464.17 mg·kg⁻¹,低于《土壤环境质量-建设用地土壤污染风险管控标准》(GB 36600-2018) 的筛选值。在两极电解液增设pH调节装置和斜板沉淀池有助于以Cr(OH)₃、Cu(OH)₂、Ni(OH)₂和Zn(OH)₂沉淀物的方式对重金属离子进行回收,阳极电解液pH控制在5.0~6.5,阴极电解液pH控制在10时,阴阳极两侧电解液中重金属沉淀回收率均达99%。增加了电解液循环的电动联合修复技术可同步实现底泥污染物的净化及回收。     

生物强化修复石油污染土壤

筛选高效石油降解菌,考察菌株的降解性能及降解机理,进行花盆模拟高效外源菌强化修复石油污染土壤实验,在降解后期添加激活剂H2O2以及木屑来试图改善微生物的修复环境,减缓微生物的衰亡,并考察修复效果。结果表明,菌株L-1的降解效果较好,其对pH和温度有较大范围的适应性,能分泌较多的表面活性物质,细胞疏水性较强。将其应用于土壤修复中,经过50 d的修复,石油残留率达到50.6%左右,生物强化比自然修复残留率降低了8%左右。在第45天添加激活剂能有效改善修复效果,70 d时添加外源菌的土样最小石油残留率达到37.9%。     

电动修复不同形态铬污染土壤的研究

研究了土壤中铬的价态对电动修复效率的影响以及电动修复前后土壤中铬形态的变化.结果表明,电动修复对于土壤中1 000 mg Cr(Ⅵ)/kg的去除效果明显,总铬去除率达59.7%;而对1 000 mg Cr(Ⅲ)/kg的去除效率较低,仅为6.2%;Cr(Ⅲ)和Cr(Ⅵ)(各500 mg/kg)同时污染的土壤,铬的去除率介于中间,为18.7%.电动修复前后,土壤中铬的形态也发生了明显的变化.其中,电动修复对土壤中Cr(Ⅵ)的提取形态影响最大,而对Cr(Ⅲ)提取形态并无太大的影响.总体上,电动修复后对于生物有效的弱酸可提取态铬的浓度都保持在较低水平,预期铬的环境风险(物理流动性和生态风险)将大大降低.     

污染土壤修复技术预测

土壤污染已成为世界性环境问题,我国土壤污染现状更为严峻。污染土壤修复技术已成为全球科技的研究重点。本研究基于该领域国内外的相关研究论文与专利,采用文献计量学的统计方法,结合国内外相关项目、计划和法规等信息,对比分析了国内外论文/专利发文量阶段变化、技术研究的首篇报道年、专利景观图等。研究结果表明,我国污染土壤修复技术研发起步较晚,与发达国家总体水平存在10~15年的差距,在产业化领域更为突出。提出了在兼顾系统集成与技术原创的条件下,我国污染土壤修复的重点研发技术,为我国土壤修复技术的发展布局与政策制定提供决策依据。     

污染土壤修复的技术再造与展望

污染土壤的面积在迅速扩大,迫切需要修复、治理;随着土壤污染组分的日益复杂化,等待着全面、高效的修复技术的研制。对污染土壤修复相关技术现状进行剖析表明,现有的各种污染土壤修复技术由于存在着许多技术上难以克服的问题,需要从技术的现有进展和技术构想进行整体意义上的创新,即如何把现有的技术进行参数优化、改造后进行最佳组合与综合,才能取得该技术领域的重大突破。污染土壤的生态化学修复,其实质在于技术的再造,代表了21世纪污染土壤修复技术的发展方向。     

鼠李糖脂协助下的土壤中镉电动修复

实验研究了重金属Cd在生物表面活性剂鼠李糖脂协助下的电动修复过程,通过不同方式、不同浓度、不同酸碱度的鼠李糖脂溶液的添加与空白处理对比,探讨了鼠李糖脂协助下电动修复过程中的Cd在土壤介质中的迁移转化和机理,分析了鼠李糖脂溶液作为电动修复添加剂的可行性。结果表明,中等浓度酸性的鼠李糖脂溶液(pH=4.78,浓度为0.5、1和2 g/L)能对土壤中的重金属Cd进行有效的富集,富集量均在初始值的4倍以上,且其可交换态比重均大于42.07%,非常有利于土壤进行二次修复。此外,以pH=4.78,浓度为0.5 g/L的鼠李糖脂溶液作为预处理剂的Ex-08中的重金属Cd并未出现富集现象,但其对重金属的Cd的总去除效率达到了49.27%。表明利用鼠李糖脂溶液作为电动修复添加剂进行土壤重金属修复是可行的。     

石油污染土壤的植物与微生物修复技术

石油污染土壤的生物修复技术具有成本低、简便高效、对环境影响小等优点,正逐步成为石油污染治理研究的热点领域,具有广阔的发展前景.介绍了我国的石油污染概况及生物修复技术在石油污染治理中的应用,重点对石油污染土壤的微生物修复、植物修复、植物一微生物联合修复技术的研究进展及各自的优点、局限性进行了综述,并提出了石油污染土壤生物修复技术研究的重点领域.     

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。     

生石灰强化机械通风法修复三氯乙烯污染土壤

机械通风法是一种操作简单、效果好、成本低的土壤修复技术,特别适合大型挥发性有机化合物(VOC)污染场地的土壤修复,但在环境温度低、土壤含水率高、土壤黏性大等情况下,其修复效果和修复周期会受到极大影响,且土壤中高浓度的污染物残留将严重影响场地修复目标的实现。为了解决这一问题,采用了在土壤中添加一定量生石灰的强化措施。结果表明:(1)生石灰可以显著提高机械通风法修复三氯乙烯(TCE)污染土壤的效果,缩短修复周期,降低污染物在土壤中的残留浓度。(2)生石灰对TCE的强化作用与生石灰的添加量和土壤类型有关,粉质黏土的强化效果要好于粉土和细砂,生石灰添加量越多,强化效果越好;(3)生石灰强化处理TCE的主要机制是提高土壤温度、降低土壤含水率、增加土壤通透性,促进土壤中TCE的解吸和挥发。     

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。     

铝酸盐材料对镉污染土壤的稳定化修复及其机理

为研究铝酸盐材料对于修复Cd污染土壤的可行性,以常见的硅酸盐材料为参照,比较了两者对土壤中Cd的稳定化效果,并对相关反应机制进行了讨论。结果表明：当土壤中Cd的质量分数为54.6 mg·kg⁻¹时,铝酸盐和硅酸盐材料使Cd的7 d浸出质量浓度分别降低58.07%~77.75%和63.46%~93.02%,180 d浸出质量浓度分别降低28.72%~79.23%和41.08%~86.63%;当土壤中Cd的质量分数为2 940.03 mg·kg⁻¹时,铝酸盐和硅酸盐材料使Cd的7 d浸出质量浓度分别降低76.97%~93.15%和19.05%~94.38%,180 d浸出质量浓度分别降低56.56%~88.87%和-32.68%~49.79%。这说明铝酸盐材料对土壤中Cd的稳定化效果优于硅酸盐材料。在CdCl₂溶液中(94.02 mg·L⁻¹),铝酸盐和硅酸盐材料分别使Cd质量浓度降低了99.92%~99.93%和99.68%~99.92%,并使pH分别增大了6.56~6.81和7.01~7.69。通过SEM-EDS、FTIR、XRD和XPS等分析手段发现,铝酸盐材料可通过水化反应生成Ca—Si—H和Ca—Al—Si—H凝胶,以实现对Cd的物理包裹和吸附,并可通过使pH增大而生成Cd(OH)₂、CdO或CdCO₃沉淀,进而实现了对Cd的稳定化。本研究表明铝酸盐材料较硅酸盐材料对Cd的稳定化更为高效且长效,可为Cd污染土壤修复提供参考。     

Combined use of a transformed red mud reactive barrier and electrokinetics for remediation of Cr/As contaminated soil

A reactive barrier (RB) of transformed red mud (TRM), a by-product of the refinement of bauxite in alumina production, was placed adjacent to the anode of an electrokinetic (EK) system with the aim of enhancing removal of chromium or arsenic, added singly to a low permeability clayey soil, and favouring entrapment. The innovative study focused on evaluation of the synergic interaction between the EK system and the RB, and of the efficiency when compared to traditional EK remediation (control tests). The results obtained underlined the successful outcome of treatment of the Cr(VI)-contaminated soil. In presence of the TRM RB, 19.4% wt. of total Cr content was detected in the anolyte and 20.6% wt. trapped in the anodic RB after 6 d, versus 6.6% wt. in the anolyte and 8.8% wt. in the soil adjacent to the anode following the control run without RB. On increasing duration of treatment up to 12 d, 60.8% wt. of total initial Cr was found in the anolyte and 25.5% wt. trapped in the RB, versus 9.1% wt. and 5.3% wt., respectively, after a control run of the same duration. Finally, on increasing the mass of TRM in the RB, 60.6% wt. of initial Cr content was found to have accumulated in the RB, with Cr being completely absent from the anodic chamber. Conversely, combined treatment was much less effective on As contaminated soil, at least under the operative conditions applied. Low initial As concentration and interference with iron oxides in the soil were likely the reasons underlying low efficiency while attempting As decontamination.     

Electrokinetic remediation of organochlorines in soil: enhancement techniques and integration with other remediation technologies

Electrokinetic remediation has been increasingly used in soils and other matrices for numerous contaminants such as inorganic, organic, radionuclides, explosives and their mixtures. Several strategies were tested to improve this technology effectiveness, namely techniques to solubilize contaminants, control soil pH and also couple electrokinetics with other remediation technologies. This review focus in the experimental work carried out in organochlorines soil electroremediation, aiming to systemize useful information to researchers in this field. It is not possible to clearly state what technique is the best, since experimental approaches and targeted contaminants are different. Further research is needed in the application of some of the reviewed techniques. Also a number of technical and environmental issues will require evaluation for full-scale application. Removal efficiencies reported in real contaminated soils are much lower than the ones obtained with spiked kaolinite, showing the influence of other factors like aging of the contamination and adsorption to soil particles, resulting in important challenges when transferring technologies into the field.     

铬污染土壤的还原稳定化修复

以湖南某工业场地的铬污染土壤为修复对象,投加不同比例的FeSO4·7H2O、FeSO4·7H2O和Ca（OH）2混合物及NaHSO3,通过测定土壤及浸出液中六价铬、总铬以及铬的形态,比较3种稳定剂对该污染土壤的还原稳定化作用。结果表明,FeSO4·7H2O和NaHSO3对铬污染土壤的还原稳定效果都较好,可以有效还原土壤中六价铬并能降低土壤中总铬的浸出浓度。当FeSO4·7H2O投加量为2%时,土壤六价铬和总铬浸出浓度降幅分别达到99.0%和57.5%;当NaHSO3投加量为0.8%时,六价铬和总铬浸出浓度降幅分别达到97.7%和42.2%,与前二者相比,FeSO4·7H2O和Ca（OH）2混合物还原稳定化效果较差。投加FeSO4·7H2O能够将土壤中活性大的可交换态和碳酸盐态铬转化为稳定的有机态和残渣态铬;而NaHSO3主要将可交换态和碳酸盐态铬转化为相对稳定的铁锰氧化态铬,其稳定化效果要差于FeSO4·7H2O。     

Anionic surfactant remediation of soil columns contaminated by nonaqueous phase liquids

A variety of column experiments have been completed for the purpose of selecting and evaluating suitable surfactants for remediation of nonaqueous phase liquids (NAPLs). The various NAPLs tested in the laboratory experiments were tetrachloroethylene (PCE), trichloroethylene (TCE), jet fuel (JP4) and a dense nonaqueous phase liquid from a site at Hill Air Force Base, UT. Both Ottawa sand and Hill field soil were used in these experiments. Surfactant candidates were first screened using phase behavior experiments and only the best ones were selected for the subsequent column experiments. Surfactants which showed high contaminant solubilization, fast coalescence times, and the absence of liquid crystal phases and gels during the phase behavior experiments were tested in soil column experiments. The primary objective of the soil column experiments was to identify surfactants that recovered at least 99% of the contaminant. The secondary objective was to identify surfactants that show low adsorption and little or no loss of hydraulic conductivity during the column experiments. Results demonstrated that up to 99.9% of the contaminants were removed as a result of surfactant flooding of the soil columns. The addition of xanthan gum polymer to the surfactant solution was shown to increase remediation efficiency as a lower volume of surfactant was required for recovering a given volume of NAPL. Based on these experimental results, guidelines for designing highly efficient and robust surfactant floods have been developed and applied to a field demonstration.     

微生物燃料电池修复石油污染盐碱土壤

生物电化学技术修复石油污染土壤并同步产出电能是一种新兴的污染土壤生态修复技术。对石油污染土壤通过其微生物燃料电池的构造,利用电化学阻抗谱分析了土壤的欧姆内阻,拟合估算了土壤的电导率,并考察了土壤微生物燃料电池的产电性能和修复效果。结果表明：采用丙酮清洗过的阳极并有水封的情况下,土壤微生物燃料电池的欧姆内阻下降了52%,电导率升高了1倍;在启动后的120 h内,最大电压和累计产出电量分别达189 mV和36 C,与对照相比分别增加了20和29倍。输出电压随着阴极与阳极之间距离的增大而减小。经过30 d的生物电化学处理,土壤中的总石油烃去除率是开路对照的3.3倍。该研究是石油污染盐碱土壤生物电化学修复的初步探索,以为污染土壤的生态修复提供新的思路。     

Accumulation of heavy metals from contaminated soil to plants and evaluation of soil remediation by vermiculite

We evaluated the distribution of 15 metal ions, namely Al, Cd, Cu, Cr, Fe, La, Mn, Ni, Pb, Sc, Ti, V, Y, Zn and Zr, in the soil of a contaminated site in Piedmont (Italy). This area was found to be heavily contaminated with Cu, Cr and Ni. The availability of these metal ions was studied using Tessier’s sequential extraction procedure: the fraction of mobile species, which potentially is the most harmful for the environment, was much higher than that normally present in unpolluted soils. This soil was hence used to evaluate the effectiveness of treatment with vermiculite to reduce the availability of the pollutants to two plants, Lactuca sativa and Spinacia oleracea, by pot experiments. The results indicated that the addition of vermiculite significantly reduces the uptake of metal pollutants by plants, confirming the possibility of using this clay in amendment treatments of metal-contaminated soils. The effect of plant growth on metal fractionation in soils was investigated. Finally, the sum of the metal percentages extracted into the first two fractions of Tessier’s protocol was found to be suitable in predicting the phytoavailability of most of the pollutants present in the investigated soil.