Ultrasonically enhanced electrokinetic remediation for removal of Pb and phenanthrene in contaminated soils

Electrokinetic and ultrasonic remediation technologies were studied for the removal of heavy metal and polycyclic aromatic hydrocarbon (PAH) in contaminated soils. The study emphasized the coupled effects of electrokinetic and ultrasonic techniques on migration as well as clean-up of contaminants in soils. The laboratory soil flushing tests combined electrokinetic and ultrasonic technique were conducted using specially designed and fabricated devices to determine the effect of both techniques. The electrokinetic technique was applied to remove mainly the heavy metal and the ultrasonic technique was applied to remove mainly organic substance in contaminated soil. A series of laboratory experiments involving electrokinetic and electrokinetic and ultrasonic flushing tests were carried out. Natural clay was used as a test specimen and Pb and phenanthrene were used as contaminants. An increase in out flow, permeability and contaminant removal rate was observed in electrokinetic and ultrasonic tests. Some practical implications of these results are discussed in terms of technical feasibility of in situ implementation of electrokinetic ultrasonic remediation technique.     

土壤修复过程中重金属形态的研究综述

重金属污染土壤的修复是现阶段污染土壤治理中的难点之一,在土壤修复过程中对重金属的形态研究已在多个领域中开展,并且在重金属形态及其与生物有效性和毒性等研究领域取得了一定的成果。本文综述了现阶段在污染土壤修复过程中对重金属形态研究的主要领域,分析研究重金属形态的必要性,总结出土壤修复过程中重金属形态方面应当从重金属在土壤与植物中的存在形态入手,研究重金属元素在不同界面间的迁移转化规律,通过阻断重金属元素在污染源、土壤、生物之间的传递链条,以阻止重金属对生物体造成危害,从而为土壤重金属污染的治理修复提供理论基础。     

MICP技术联合多孔硅吸附材料对锌铅复合污染土固化/稳定化修复的试验研究

近年来,工业和科技的快速发展使得重金属污染土固化/稳定化的修复研究成为热点。运用微生物诱导碳酸钙沉淀(MICP)技术联合吸附材料对锌铅复合重金属污染土进行固化/稳定化的修复,通过无侧限抗压强度试验、毒性浸出试验,评价处理前后污染土的固化效果与重金属的稳定化效果,结合扫描电镜(SEM)和X射线衍射(XRD)等检测手段,揭示MICP技术处理锌铅重金属污染土的修复机制。研究结果表明,采用MICP技术对锌铅重金属污染土进行固化/稳定化之后,可以有效降低污染土中有害重金属的浸出性。当矿化时间为10d时,试样无侧限抗压强度为942.5k Pa;铅的浸出浓度为4.20mg/L,比未处理时降低了44.81%;锌的浸出浓度为4.31mg/L,比未处理时降低了46.19%,效果显著。在此基础上,添加10%的多孔硅吸附材料后,试样无侧限抗压强度可达到1 021 kPa,强度提高了8.3%;铅的浸出浓度为2.45mg/L,与未经处理时相比,降幅达到了67.81%,与单纯MICP方法处理时相比,铅浸出浓度被二次降低了41.67%;锌的浸出浓度仅为2.93 mg/L,与未经处理时相比,降幅达到了63.4%,与单纯...     

Atmospheric pressure dielectric barrier discharge for the remediation of soil contaminated by organic pollutants

The remediation of soil, contaminated by organic pollutants, in a cylinder-to-plane dielectric barrier discharge reactor at atmospheric air pressure was reported. Two model organic pollutants were selected; a solid pollutant (2,6-dichloropyridine) and a liquid pollutant (n-dodecane). The effects of the contaminant’s initial concentration and state, the energy consumption, and the soil type on the pollutant removal efficiency were investigated. To that scope, various contaminated samples of both quartz sand and loamy sandy soil were treated by plasma for various treatment times and initial 2,6-dichloropyridine/n-dodecane concentrations. The results revealed that (1) the removal efficiency of 2,6-dichloropyridine was higher compared to that of n-dodecane at a given plasma treatment time and (2) the removal efficiency increased with the energy density increasing, but decreased as the soil heterogeneity, organic matter and pollutant concentration were enhanced. The main removal mechanism proposed is the evaporation of pollutant molecules coupled with their oxidation by plasma species in the gas and solid/liquid phase.     

碱改性凹凸棒石对土壤中镉化学形态及环境风险的影响

凹凸棒石进行碱改性后性能的提高,为其钝化修复重金属污染土壤提供重要基础.本文采用不同比例的氢氧化钠对凹凸棒石进行改性,利用扫描电镜(SEM)、X射线衍射(XRD)和傅里叶变换红外光谱法(FTIR)分析改性前后凹凸棒石理化特性的变化,并在人工配制的重金属Cd污染土壤上进行钝化实验,研究氢氧化钠改性凹凸棒石对污染土壤中Cd...     

冻结技术在水土重金属污染净化与修复中的应用及进展

随着工业化进程的加快,水土重金属污染事件逐渐增多,对其治理与修复成为当前的迫切工作。冻结技术在治理修复污染水土时,其修复过程只向地层输入“冷量”,属于绿色修复技术,无二次污染风险,受到越来越多的关注。详细总结了冻结技术的修复机理,及其在污水、污泥、重金属污染土壤治理修复中的应用现状和最新研究进展。冻结修复机理是通过冰的自净作用和固-液相平衡原理来实现污染物的定向驱赶和富集,而黏性土壤颗粒的吸附和阻滞作用使单一技术对重金属污染土壤的修复难度增大,其他修复手段与冻结技术联合处理成为一种新的思路。利用冻结土体的低渗透性,还可有效降低污染物的迁移速度,封闭不同种类污染物,形成阻隔污染物扩散的冻结屏障。冻结修复技术在水土重金属污染净化及修复领域具有良好的应用前景。     

发扬地学学科优势,形成具有国土资源部门特色的土壤修复理论与技术体系

岩石圈是土壤重金属元素的根本来源,是其迁移转化和生物-地球化学循环的场所,也是重金属元素的最后归宿,因此地质学、岩石学、矿物学和地球化学在重金属污染土壤修复中具有基础性的重要指导意义。国土资源部门已经在土壤重金属调查、溯源和风险评价上发挥了重要作用,还可以在探索研究灾害链的组成、影响因素和阻断途径的基础上,形成有地学特色的修复理论和技术。目前,国土资源部门的修复理论研究成果主要集中在缓变型地球化学灾害理论和地球化学工程学方面,在所属研究机构已经形成了若干种土壤修复剂,通过小试、中试和典型示范,验证了这些修复剂具有优异的修复性能与效果,是落实"土十条"和生态文明建设的一支重要力量。     

Remediation of saturated Shanghai sandy silt contaminated with p-xylene using air sparging

Air sparging is an effective technique for the remediation of soil and groundwater polluted by volatile organic compounds. In this paper, this technique was investigated by conducting air-sparging test in the laboratory on the Shanghai sandy silt that was artificially contaminated with p-xylene. A test tank was designed for this purpose. During the air-sparging process, aqueous p-xylene solutions were extracted from the observation holes, and their concentrations were quantified by the spectrophotometric detection method. The mechanism of mass transfer process of p-xylene in the vicinity of sparging well and the remediation of the contaminated groundwater by air sparging were explored. The results showed that the removal zone of the p-xylene was mainly located within a radius of about 20?cm around the air injection well, with 90?% p-xylene removed after 20-day air sparging. Within the initial 5-day sparging, the concentration of p-xylene decreased rapidly in the mass transfer zone. By contrast, in the area far from the injection well, the p-xylene concentration decreased evenly and slowly. Thus, the remediation of contaminated soil and groundwater by air sparging is space?Ctime dependent. For further analysis, the adsorption of silt was taken into account, and the distribution coefficient, K _d , was introduced to the modified Shackleford??s mass transfer model. The comparison between the simulated and measured results indicates that the modified model can satisfactorily describe the p-xylene mass transfer observed in this study.     

Heavy metal accumulation in soil after application of organic wastes

Municipal solid waste compost and cattle manure are used as organic fertilizers in agriculture and horticulture. These wastes, however, may also have some negative effects on the agricultural environment. This study investigates the effects of municipal solid waste compost of Kerman (MSC) and cattle manure (CM) on availability of the heavy metal in calcareous soil (extractable with EDTA) in greenhouse conditions. The MSC and CM were mixed thoroughly with soil at rates of 0%, 2%, and 4% of dry matter. After 90 days of incubation, the soil samples were analyzed. Addition of levels of each two organic wastes into soil significantly decreased the soil pH and increased the soil EC as compared with control (unamended soil).The available contents (EDTA-extractable) of Cd, Pb, Cu, Zn, and Cu in the soil samples were increased because of each two organic treatments applied. The heavy metal contents in the soil samples amended with MSC were more than CM. The heavy metal contents of organic wastes were well below the maximum allowed by USEPA. It is recommended that in Iran, the legal maximum permissible limit for heavy elements in organic wastes must be determined.     

Sorption of surfactants and personal care products in Indian soils

Sorption of three surfactants and personal care products in four types of commonly occurring Indian soils was extensively studied. The soils used in the study were red soil, clay soil, compost soil and sandy soil as classified by American Society for Testing and Materials (ASTM). The three surfactants used in the study were representative of cationic, non-ionic and anionic surfactant groups. The sorption of surfactants followed the descending order: sodium dodecyl sulphate (SDS) > trimethyl amine (TMA) > propylene glycol (PG). The maximum adsorption capacity (Q_max) was obtained in compost soil (28.6 mg/g for SDS; 9.4 mg/g for TMA and 4 mg/g for PG). The rate of adsorption was the maximum in compost soil followed by clay and red soils, and minimum for sandy soils. It is found that the Freundlich model fits the isotherm data better than the Langmuir model. Freundlich coefficient (K _f) increased as the organic content of soils increased. Desorption of target pollutants in tap water was 20–50% whereas acid desorbs 40–90% of target pollutants from soil matrix. It was also found that the adsorption and desorption were significantly affected by the presence of clay and organic matter. The results also indicate that surfactants and personal care products, especially TMA and PG, are highly mobile in sandy soil followed by red soil. Therefore, immobilization of target pollutants is most economical and effective in compost and clayey soils whereas for other type of soils the combination of physiochemical and biological process will be effective option for remediation.     

有机物污染的土壤治理方法及研究进展

污染土壤的修复已成为环境保护研究的一个重点。本基干有机物污染土壤治理的最新进展,介绍有机物污染土壤的物理、化学、生物、植物治理方法。并讨论了各种治理方法的最新动态与存在问题。     

Surfactant-enhanced remediation of contaminated soil: a review

Extracting aqueous solutions with or without additives are employed to solubilize contaminants in soil. Since water solubility is the controlling removing mechanism, additives are used to enhance efficiencies. These additives can reduce the time to treat a site compared to the use of water alone. Additives must be of low toxicity and biodegradable. The research in this area has focussed mainly on halogenated volatile organic compounds (VOCs) and is still quite limited for metal removal. Additives include surfactants, organic and inorganic acids, sodium hydroxide, which can dissolve organic soil matter, water-soluble solvents such as methanol, displacement of cations with nontoxic ones, complexing agents such as EDTA, acids in combination with complexing agents or oxidizing/reducing agents. Cationic, anionic and nonionic surfactants are particularly used for soil washing or flushing. They contain both hydrophobic and hydrophilic portions, making them ideal for solubilization of hydrophobic compounds. Numerous studies have indicated that surfactants enhance recoveries of non-aqueous phase liquids (NAPLs). There have also been indications that pretreatment of soil with surfactant washing to solubilize hydrophobic compounds such as PAHs enhances biodegradation of these contaminants. A few in situ field studies have been performed with surfactants. Large-scale treatment has been done mostly for organic removal. Soil pH, soil type, cation exchange capacity (CEC), particle size, permeabilities and contaminants all affect removal efficiencies. High clay and organic matter contents are particularly detrimental. Understanding the chemistry of the binding of the contaminant and the hydrogeology of the site are very important. Once the water is pumped from the soil, it must be extracted and then treated to remove the hydrocarbons and metals. Several technologies exist such as sodium hydroxide or sodium sulfide precipitation, ion exchange, activated carbon adsorption, ultrafiltration, reverse osmosis, electrodialysis and biological processes. Recycling of the surfactants is desired to decrease treatment costs.

This paper will provide an overview of the laboratory research, field demonstration and full-scale application of surfactants for the remediation of contaminated soil. The majority of pilot scale in situ flushing tests, particularly in the United States, have involved the use of surfactants and co-solvents. There are only a few full-scale projects however. Recent laboratory scale efforts by the authors concerning the use of biosurfactants, biologically produced surfactants, to enhance the removal of copper, cadmium and zinc from contaminated soils and sediments are discussed. Three types of biosurfactants were evaluated for their effectiveness. They included a lipopeptide called surfactin from Bacillus subtilis, a rhamnolipid from Pseudomonas aeruginosa and a sophorolipid from Torulopsis bombicola. The results indicated the feasibility of removing the metals with the anionic biosurfactants even though the exchangeable fractions were not significant.     

Determination of adsorption efficiency based on cation exchange capacity related to red earth, bone meal and pulverised fly ash as ameliorants to lead contaminated soils

Efficient treatment strategies to reduce the toxicity of metal contaminated soil using cost effective techniques such as naturally available ameliorants and industrial waste have emerged. Three easily available amendments were determined: Bone meal, red earth/mud and pulverised fly ash (PFA). The application of ameliorants offered a possible alternative in situ remediation of contaminated sites without disruption to the ecosystem profile. In comparison to other ameliorants Red earth/mud was found to be efficient in intercepting lead leaching from soil amended with different lead compounds based on CEC (Cmol/g). This was associated with the heterogeneous adsorbency principle in red mud which is associated with its ability to bind metal ions (M²⁺) onto one or two types of surface sites at pH< 6.0. However areas that need to be studied and assessed (for public health concerns) critically for wide spread application of all the ameliorants include off-site effects of the ameliorants.     

土壤类型及组分对热活化过硫酸盐氧化降解土壤中挥发性氯代烃的影响

为了探究高级氧化技术对土壤中有机氯代烃的氧化降解作用,为ISCO（in situ chemical oxidation）技术体系提供重要的理论依据和数据支撑,考察了热活化过硫酸盐（persulfate,PS）氧化降解不同类型土壤（砂类土壤、黏土类土壤）中挥发性氯代烃污染物（三氯乙烯（TCE）、三氯乙烷（TCA）、顺式-1,2-二氯乙烯（cis-1,2-DCE）、1,2-二氯乙烷（1,2-DCA））的效能;同时,通过硫酸盐与土壤相互作用过程研究,探究了不同土壤介质中有机质和无机组分在过硫酸盐消耗中所占比例。结果表明：在50℃时,热活化过硫酸盐可有效降解土壤中1,2-DCA、cis-1,2-DCE、TCA和TCE,砂类土壤介质中4种氯代烃降解效果依次为25%、89%、5%和61%,黏土类土壤介质中4种氯代烃降解效果依次为35%、86%、8%和63%;4种氯代烃的降解效果从高到低顺序依次为cis-1,2-DCE、TCE、1,2-DCA、TCA,砂类土壤中的氯代烃总体降解效果优于黏土类土壤中氯代烃的降解效果。另外,土壤中过硫酸盐氧化降解氯代烃反应研究发现,砂类和黏土类土壤介质组分中有机质消耗率分别为81.3%和72.6%,铁元素消耗率分别为80.5%和38.6%,表明土壤介质组分与过硫酸盐发生了氧化还原反应,从而导致过硫酸盐自身的大量消耗。由此可知,土壤介质中的有机质、铁元素等矿物质均参与过硫酸盐的消耗过程,且土壤有机质、铁元素与氯代烃之间在消耗过硫酸盐反应上存在竞争关系,土壤组分过多地消耗了过硫酸盐,导致了氯代烃的氧化降解效率较低。因此,针对实际有机氯代烃污染场地,采用过硫酸盐氧化技术进行修复时,过硫酸盐的实际投加量要远高于化学计量值,需充分考虑到土壤组分对过硫酸盐自身的消耗作用。     

凹凸棒石用于修复铜锌镉重金属污染土壤的研究

利用凹凸棒石黏土矿物优异的物化性能对采集的安徽铜陵地区重金属污染土壤进行盆栽修复试验,以降低种植蔬菜中重金属污染物的有效态含量。凹凸棒石与矿区土壤的质量配比设置5组(1∶10、1∶20、1∶40、1∶100以及原土),选择适宜在北京生长的四季小白菜和北京快菜进行种植,盆栽试验结果表明,使用凹凸棒石黏土矿物可以将土壤的pH值提高到5～8,改善了矿区的土壤环境条件,提高黏土矿物对重金属的吸附性能;通过适量添加凹凸棒石黏土矿物,对Cu元素的平均修复率达到31.50%,Zn元素的平均修复率达到26.15%,Cd元素的平均修复率达到34.92%,能够有效减少蔬菜对Cu、Zn、Cd三种重金属元素的吸收。凹凸棒石与土壤的质量比为1∶20时,对污染土壤的修复效果最佳。     

An assessment of the utilization of waste resources for the immobilization of Pb and Cu in the soil from a Korean military shooting range

Military shooting range soils contaminated by heavy metals have been subjected to remediation efforts to alleviate the detrimental effects of exposure on humans and the surrounding environment. Waste materials can be used as cost-effective soil amendments to immobilize heavy metals in contaminated soils. In this study, naturally occurring lime-based waste materials including egg shells, oyster shells, and mussel shells were assessed for their effectiveness toward heavy metal immobilization in military shooting range soil in Korea. Soil was treated in batch leaching experiments with 0, 2.5, 5, 10, and 15% of each lime-based waste material. The results showed that the lime-based waste materials effectively reduced water-soluble Pb at an application rate of 2.5% by weight of the soil. Increase in soil pH from 6.6 to 8.0 was considered to be the main chemistry of Pb immobilization, which was supported by the formation of insoluble Pb species at high pH values as confirmed by the visual MINTEQ thermodynamic model. In contrary, water-soluble Cu was increased in the lime-based waste material-treated soils when compared to the untreated soil. This was likely attributed to the formation of soluble Cu?CDOC (dissolved organic carbon) complexes as all lime-based waste materials applied increased DOC contents in the soil. Therefore, care must be taken in selecting the appropriate amendment for immobilizing metals in shooting range soils.     

Adsorption of dissolved organic matter on clay minerals as assessed by infra-red, CPMAS C NMR spectroscopy and low field T1 NMR relaxometry

Dissolved organic matter (DOM) is a very important environmental constituent due to its role in controlling factors for soil formation, mineral weathering and pollutant transport in the environment. Prediction of DOM physical-chemical properties is achieved by studying its chemical structure and spatial conformation. In the present study, dissolved organic matter extracted from compost obtained from the organic fraction of urban wastes (DOM-P) has been analysed by FT-IR, CPMAS ¹³C NMR spectroscopy and ¹H T₁ NMR relaxometry with fast field cycling (FFC) setup. While the first two spectroscopic techniques revealed the chemical changes of dissolved organic matter after adsorption either on kaolinite (DOM-K) or montmorillonite (DOM-S), the latter permitted the evaluation of the conformational variations as assessed by longitudinal relaxation time (T₁) distribution at the fixed magnetic field of 500 mT. Alterations of T₁ distributions from DOM-P to DOM-K and DOM-S were attributed to a decreasing molecular complexity following DOM-P adsorption on the clay minerals. This study applied for the first time solid state ¹H T₁ NMR relaxometry to dissolved organic matter from compost obtained from the organic fraction of urban wastes and revealed that this technique is very promising for studying environmentally relevant natural organic systems.     

Effects of in situ remediation on the speciation and bioavailability of zinc in a smelter contaminated soil

We report results from an extensive study on the speciation of zinc (Zn) and its relation to the mobility and bioavailablity of this element in a smelter contaminated soil and an in situ remediated area of this soil 12 yr after the application of cyclonic ash and compost. Emphasis was placed on the role of neoformed precipitates in controlling Zn speciation, mobility and bioavailability under different environmental conditions. Twelve years after remediation, the pH of the treated and non-treated soil differed by only 0.5 pH unit. Using state-of-the-art electron and X-ray microscopies in combination with micro-focused extended X-ray absorption fine structure (μ-EXAFS) spectroscopy, no major differences in Zn speciation were found between samples of the treated and non-treated soil. In both soils, 30% to 50% of Zn was present in smelter related minerals (willemite, hemimorphite or gahnite), while 50% to 70% of Zn was incorporated into newly formed Zn precipitates. Contrary to the non-treated soil, the treated soil did not contain gahnite or sphalerite; it is possible that these minerals were dissolved under the higher pH conditions at the time of treatment. Desorption experiments, using a stirred flow technique with a 0.1 mol/L CaCl₂ (pH 6.5) and a HNO₃ (pH 4.0) solution were employed to determine the exchangeable Zn fraction and the Zn fraction which will be mobilized under more extreme weathering conditions, respectively. No significant differences were found in desorption behavior between the treated vs. non-treated soil. Bioavailability tests, using the R. metallidurans AE1433 biosensor showed that ∼8% of total Zn was bioavailable in both the treated and non-treated soils. It was concluded that the incorporation of Zn into newly formed precipitates in both the treated and non treated soils leads to a significant natural attenuation of the exchangeable/bioavailable Zn fraction at near neutral pH conditions. At lower pHs, conditions not favorable to the formation of Zn precipitates, the pool of Zn associated with the secondary Zn precipitates is potentially more bioavailable.     

Source and remediation for heavy metals of soils at an iron mine of Ulsan City,Korea

Ulsan mine produced the iron ore minerals of magnetite, arsenopyrite, and scheelite in 1992, and serpentine was developed from 1977 to 2002. The soils of the mine were contaminated by heavy metals such as As, Zn, Ni, and Cd. Heavy metals of Ni and Zn came mostly from serpentinite, and As was derived mainly from arsenopyrite in the scan-type iron ore body. As, Zn, and Ni were major contaminants, but Cd was a minor contaminant on a basis of Korean standard. The heavy metals in the deep depth (>?5 m) came from the host rocks, and those in the shallow depth (<?5 m) were derived from the organic–mineral complexation soil. The remediation plan was a soil washing for highly contaminated soils and the containment of clay materials for less contaminated soils. Even though the remediation methods were successful, the continuous monitoring and the analysis of monitoring data are still necessary for the conservation of soil and groundwater around the study area.     

淋洗剂乙二胺四乙酸对重金属污染土工程特性的影响

以重金属铅（Pb2+）污染土和淋洗剂乙二胺四乙酸（EDTA）为研究对象,通过批次试验研究了不同浓度EDTA的淋洗对Pb2+污染土的渗透特性、持水特性、压缩特性、抗剪强度等工程特性的影响,为淋洗修复后土壤的二次利用提供参数支持。基于矿物成分、孔隙结构等微观试验,揭示了土壤工程特性变化的内在机制。研究结果表明,当淋洗剂EDTA浓度从0增加到0.15 mol/L,经淋洗修复后的污染土壤pH值从7.94下降到5.12,渗透系数降低超过一个数量级,黏聚力降低50%以上,而内摩擦角增大,持水性能提高,孔隙比从0.81下降到了0.76。微观试验的结果表明,随着淋洗剂浓度的增大,土壤中的蒙脱石、钠长石和伊利石矿物含量减少,石英矿物含量增加,其中蒙脱石含量从7.87%下降到了0.07%,而石英矿物含量增加了11.09%;淋洗后土壤单位质量进汞量由0.22 ml/g降低到0.15 ml/g,土壤总孔隙体积减少。重金属污染土淋洗修复工程在考虑重金属去除率及经济性指标的同时,还应考虑淋洗剂对土壤工程特性的弱化。