Soil remediation time to achieve clean-up goals II: Influence of natural organic matter and water contents

This work reports a relatively rapid procedure for the forecasting of the remediation time (RT) of sandy soils contaminated with cyclohexane using vapour extraction. The RT estimated through the mathematical fitting of experimental results was compared with that of real soils. The main objectives were: (i) to predict the RT of soils with natural organic matter (NOM) and water contents different from those used in experiments; and (ii) to analyse the time and efficiency of remediation, and the distribution of contaminants into the soil matrix after the remediation process, according to the soil contents of: (ii1) NOM; and (ii2) water. For sandy soils with negligible clay contents, artificially contaminated with cyclohexane before vapour extraction, it was concluded that: (i) if the NOM and water contents belonged to the range of the prepared soils, the RT of real soils could be predicted with relative differences not higher than 12%; (ii1) the increase of NOM content from 0% to 7.5% increased the RT (1.8-13 h) and decreased the remediation efficiency (RE) (99-90%) and (ii2) the increase of soil water content from 0% to 6% increased the RT (1.8-4.9 h) and decreased the RE (99-97%). NOM increases the monolayer capacity leading to a higher sorption into the solid phase. Increasing of soil water content reduces the mass transfer coefficient between phases. Concluding, NOM and water contents influence negatively the remediation process, turning it less efficient and more time consuming, and consequently more expensive.     

Soil remediation time to achieve clean-up goals I: Influence of soil water content

The current models are not simple enough to allow a quick estimation of the remediation time. This work reports the development of an easy and relatively rapid procedure for the forecasting of the remediation time using vapour extraction. Sandy soils contaminated with cyclohexane and prepared with different water contents were studied. The remediation times estimated through the mathematical fitting of experimental results were compared with those of real soils. The main objectives were: (i) to predict, through a simple mathematical fitting, the remediation time of soils with water contents different from those used in the experiments; (ii) to analyse the influence of soil water content on the: (ii(1)) remediation time; (ii(2)) remediation efficiency; and (ii(3)) distribution of contaminants in the different phases present into the soil matrix after the remediation process. For sandy soils with negligible contents of clay and natural organic matter, artificially contaminated with cyclohexane before vapour extraction, it was concluded that (i) if the soil water content belonged to the range considered in the experiments with the prepared soils, then the remediation time of real soils of similar characteristics could be successfully predicted, with relative differences not higher than 10%, through a simple mathematical fitting of experimental results; (ii) increasing soil water content from 0% to 6% had the following consequences: (ii(1)) increased remediation time (1.8-4.9h, respectively); (ii(2)) decreased remediation efficiency (99-97%, respectively); and (ii(3)) decreased the amount of contaminant adsorbed onto the soil and in the non-aqueous liquid phase, thus increasing the amount of contaminant in the aqueous and gaseous phases.     

Remediation efficiency of vapour extraction of sandy soils contaminated with cyclohexane: Influence of air flow rate, water and natural organic matter content

This work reports the analysis of the efficiency and time of soil remediation using vapour extraction as well as provides comparison of results using both, prepared and real soils. The main objectives were: (i) to analyse the efficiency and time of remediation according to the water and natural organic matter content of the soil; and (ii) to assess if a previous study, performed using prepared soils, could help to preview the process viability in real conditions. For sandy soils with negligible clay content, artificially contaminated with cyclohexane before vapour extraction, it was concluded that (i) the increase of soil water content and mainly of natural organic matter content influenced negatively the remediation process, making it less efficient, more time consuming, and consequently more expensive; and (ii) a previous study using prepared soils of similar characteristics has proven helpful for previewing the process viability in real conditions.     

The use of maize and poplar in chelant-enhanced phytoextraction of lead from contaminated agricultural soils

Chelant-enhanced phytoextraction of heavy metals is an emerging technological approach for a non-destructive remediation of contaminated soils. The main objectives of this study were (i) to assess the extraction efficiency of two different synthetic chelating agents (ethylenediaminetetraacetic acid (EDTA) and ethylenediaminedisuccinic acid (EDDS)) for desorbing Pb from two contaminated agricultural soils originating from a mining and smelting district and (ii) to assess the phytoextraction efficiency of maize (Zea mays) and poplar (Populus sp.) after EDTA application. EDTA was more efficient than EDDS in desorbing and complexing Pb from both soils, removing as much as 60% of Pb. Maize exhibited better results than poplar when extracting Pb from the more acidic (pH approximately 4) and more contaminated (up to 1360 mg Pb kg(-1)) agricultural soil originating from the smelting area. On the other hand, poplars proved to be more efficient when grown on the near-neutral (pH approximately 6) and less contaminated (up to 200 mg Pb kg(-1)) agricultural soil originating from the mining area. Furthermore, the addition of EDTA led to a significant increase of Pb content especially in poplar leaves, proving a strong translocation rate within the poplar plants.     

Model analysis of mechanisms controlling pneumatic soil vapor extraction

The efficiency of traditional soil venting or soil vapor extraction (SVE) highly depends on the architecture of the subsurface because imposed advective air flow tends to bypass low-permeable contaminated areas. Pneumatic SVE is a technique developed to enhance remediation efficiency of heterogeneous soils by enforcing large fluctuating pressure fronts through the contaminated area. Laboratory experiments have suggested that pneumatic SVE considerably improves the recovery rate from low-permeable units. We have analyzed the experimental results using a numerical code and quantified the physical processes controlling the functioning of the method. A sensitivity analysis for selected boundary conditions, initial conditions and parameters was carried out to examine how the method behaves under conditions different from the experimental set-up. The simulations show that at the laboratory level the pneumatic venting technology is superior to the traditional technique, and that the method is particularly efficient in cases where large permeability contrasts exist between soil units in the subsurface.     

有机污染土壤通风去污技术研究进展

土壤气体抽排净化技术是一种安全、高效、经济的有机污染土壤治理技术。本文系统分析了土壤气体抽排净化技术的特点、现状及发展趋势 ;总结了估算污染物净化时间的数学模型 ;概括了影响土壤气体抽排净化技术净化时间的主要因素 ,包括土壤透气率、含水率、有机污染物气体饱和蒸气压、抽排流速、环境温度 ;本文还对目前土壤气体抽排净化技术需要研究的问题及发展前景进行了展望。     

Dissolution and removal of PAHs from a contaminated soil using sunflower oil

This study reports on the feasibility of remediation of polycyclic aromatic hydrocarbon (PAH) contaminated soils using sunflower oil, an environmentally-friendly solvent. Batch experiments were performed to test the influence of oil/soil ratio on the remediation of PAH contaminated soil, and to test the mass transfer behaviors of PAHs from soil to oil. An empirical model was employed to describe the kinetics of PAH dissolution and to predict equilibrium concentrations of PAHs in oil. PAH containing oil was regenerated using active carbon. Results show that dissolution of PAHs from a Manufactured Gas Plant (MGP) soil at oil/soil ratios of one or two were almost the same. Nearly all PAHs (81-100%) could be removed by sunflower oil dissolution. Mass transfer coefficients for low molecular PAHs namely fluoranthene, phenanthrene and anthracene were one or two orders of magnitude higher than those for high molecular PAHs with 4-6 rings. Ninety milliliters of PAH containing oil could be regenerated by 10 g active carbon in a batch reactor. Such a remediation procedure indicates that sunflower oil is a promising agent for the removal of PAHs from MGP soils. However, further research is required before the method can be used for in situ remediation of contaminated sites.     

Bioremediation of soil contaminated with polynuclear aromatic hydrocarbons (PAHs): a review

Polynuclear aromatic hydrocarbons (PAHs) constitute a group of priority pollutants which are present at high concentrations in the soils of many industrially contaminated sites. Criteria established for the removal or treatment or both of soils contaminated with PAHs vary widely within and between nations. The bioremediation of contaminated soils with in-situ, on-site, and bioreactor techniques is reviewed, together with the factors affecting PAH degradation. Current in-situ remediation techniques are considered ineffective for the removal of most PAHs from contaminated soil. On-site 'landforming' methods have been used successfully (and within a reasonable period of time) to degrade only those PAHs with three or fewer aromatic rings. Bioreactors have proved most effective for soil remediation, since conditions for enhanced degradation can be achieved most readily. However, bioreactors are still at the development stage, and further research is required to optimise their efficiency and economy for routine use. Degradation of the more recalcitrant high-molecular-weight PAHs is contaminated soil has not been particularly successful to date. Further research needs are identified to help develop bioremediation into a most cost-effective technology. The importance of full site assessments and treatability studies for successful application in the field is emphasised.     

土壤柴油污染修复的抽气提取去除实验研究

为得到土壤气相抽提(SVE)去除柴油的优化条件,进行了一维土柱抽气提取去除柴油污染物的实验研究,研究不同初始含水率、不同抽气量对污染土壤中柴油去除率的影响及不同深度残留柴油的变化规律。结果表明：在本实验模拟的范围内,抽气量越大,SVE处理效果越好;初始含水率越低,处理效果越好;此外,不同深度去除率变化的规律基本上是随深度的增大而减小。实验结果可为土壤轻油污染实际治理提供实验数据基础。     

Influence of surfactant sorption on the removal of phenanthrene from contaminated soils

Laboratory column flushing experiments were conducted to remove phenanthrene from contaminated soils by Triton X-100 (TX100) with an aim to investigating the effect of surfactant sorption on the performance of surfactant-enhanced remediation process. The effluent concentration of phenanthrene from soil columns showed strong dependence on the sorption breakthrough curves of TX100. The removal of phenanthrene from contaminated soils was enhanced only when the sorption breakthrough of TX100 occurred and the influent concentration of TX100 was greater than the critical enhanced flushing concentration (CEFC). The sorption of surfactant onto soils and the subsequent partitioning of contaminants into soil-sorbed surfactant had a significant effect on the solute equilibrium distribution coefficient (KD) and thus the flushing efficiency for phenanthrene. A model was developed to predict KD and CEFC values for simulating the performance of surfactant-enhanced flushing for contaminated soils. These results are of practical interest in developing effective and safe surfactant-enhanced remediation technologies.     

Effect of hydrocarbon pollution on the microbial properties of a sandy and a clay soil

The aim of this work was to ascertain the effects of different types of hydrocarbon pollution on soil microbial properties and the influence of a soil's characteristics on these effects. For this, toxicity bioassays and microbiological and biochemical parameters were studied in two soils (one sandy and one clayey) contaminated at a loading rate of 5% and 10% with three types of hydrocarbon (diesel oil, gasoline and crude petroleum) differing in their volatilisation potential and toxic substance content. Soils were maintained under controlled conditions (50-70% water holding capacity, and room temperature) for six months and several microbiological and toxicity parameters were monitored 1, 60, 120 and 180 days after contamination. The toxic effects of hydrocarbon contamination were greater in the sandy soil. Hydrocarbons inhibited microbial biomass, the greatest negative effect being observed in the gasoline-polluted sandy soil. In both soils crude petroleum and diesel oil contamination increased microbial respiration, while gasoline had little effect on this parameter, especially in the sandy soil. In general, gasoline had the highest inhibitory effect on the hydrolase activities involved in N, P or C cycles in both soils. All contaminants inhibited hydrolase activities in the sandy soil, while in the clayey soil diesel oil stimulated enzyme activity, particularly at the higher concentration. In both soils, a phytotoxic effect on barley and ryegrass seed germination was observed in the contaminated soils, particularly in those contaminated with diesel or petroleum.     

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.     

Kinetic constraints on theIn-situ remediation of soils contaminated with organic chemicals

Cleanup of contaminated soils to comply with soil quality limits currently receives much interest.In-situ remediation of contaminated soils relies on the ability of the techniques employed to enhance the rate of release of contaminants from the soil-sorbed and nonaqueous phase liquid (NAPL) phases into the aqueous or gaseous phases from which they can be more readily removed and treated. Contaminant concentrations in these “environmentally mobile” forms usually decline over time so that the economic efficiency and the overall success of remediation technologies are subject to the “law of diminishing returns”. In this paper we consider the “state of the art” in our understanding of NAPL dissolution and transport, desorption of soilsorbed contaminants and fluid flow in porous media. The extent to which these processes may constrain the success of bioremediation, pump-and-treat remediation and soil venting in relation to established soil quality limits is addressed. Finally, we suggest directions for future research and comment on legislative considerations.     

Mobilization of phenol and dichlorophenol in unsaturated soils by non-uniform electrokinetics

The poor mobility of organic pollutants in contaminated sites frequently results in slow remediation processes. Organics, especially hydrophobic compounds, are generally retained strongly in soil matrix as a result of sorption, sequestration, or even formation into non-aqueous-phase liquids and their mobility is thus greatly reduced. The objective of this study was to evaluate the feasibility of using non-uniform electrokinetic transport processes to enhance the mobility of organic pollutants in unsaturated soils with no injection reagents. Phenol and 2,4-dichlorophenol (2,4-DCP), and kaolin and a natural sandy loam soil were selected as model organics and soils, respectively. The results showed that non-uniform electrokinetics can accelerate the desorption and movement of phenol and 2,4-DCP in unsaturated soils. Electromigration and electroosmotic flow were the main driving forces, and their role in the mobilization of phenol and 2,4-DCP varied with soil pH. The movement of 2,4-DCP in the sandy loam towards the anode (about 1.0 cmd(-1)V(-1)) was 1.0-1.5 cmd(-1)V(-1) slower than that in the kaolin soil, but about 0.5 cmd(-1)V(-1) greater than that of phenol in the sandy loam. When the sandy loam was adjusted to pH 9.3, the movement of phenol and 2,4-DCP towards the anode was about twice and five times faster than that at pH 7.7, respectively. The results also demonstrated that the movement of phenol and 2,4-DCP in soils can be easily controlled by regulating the operational mode of electric field. It is believed that non-uniform electrokinetics has the potential for practical application to in situ remediation of organics-contaminated sites.     

Removal of polycyclic aromatic hydrocarbons from manufactured gas plant-contaminated soils using sunflower oil: laboratory column experiments

Laboratory column experiments were performed to remove PAHs (polycyclic aromatic hydrocarbons) from two contaminated soils using sunflower oil. Two liters of sunflower oil was added to the top of the columns (33 cm x 21 cm) packed with 1 kg of PAH-contaminated soil. The sunflower oil was applied sequentially in two different ways, i.e. five additions of 400 ml or two additions of 1l. The influence of PAH concentration and the volume of sunflower oil on PAH removal were examined. A soil respiration experiment was carried out and organic carbon contents of the soils were measured to determine degradability of remaining sunflower oil in the soils. Results showed that the sunflower oil was effective in removing PAHs from the two soils, more PAHs were removed by adding sunflower oil in two steps than in five steps, probably because of the slower flow rate in the former method. More than 90% of total PAHs was removed from a heavily contaminated soil (with a total 13 PAH concentration of 4721 mg kg(-1)) using 4 l of sunflower oil. A similar removal efficiency was obtained for another contaminated soil (with a total 13 PAH concentration of 724 mg kg(-1)), while only 2l was needed to give a similar efficiency. Approximately 4-5% of the sunflower oil remained in the soils. Soil respiration curves showed that remaining sunflower oil was degraded by allowing air exchange and supplying with nutrients. Organic carbon content of the soil was restored to original level after 180 d incubation. These results indicated that the sunflower oil had a great capacity to remove PAHs from contaminated soils, and sunflower oil solubilization can be an alternative technique for remediation of PAH contaminated soils.     

污染土壤的淋洗法修复研究进展

污染土壤淋洗技术是修复污染土壤的一种新方法 ,是对污染土壤生物修复的一种补充 ,使污染土壤修复的系统化成为可能。淋洗法主要使用淋洗剂清洗土壤 ,使土壤中污染物随淋洗剂流出 ,然后对淋洗剂及土壤进行后续处理 ,从而达到修复污染土壤的目的。因为淋洗剂的种类和淋洗方式的不同 ,土壤淋洗法可分为许多种类。土壤淋洗法主要受土壤条件、污染物类型、淋洗剂的种类和运行方式等因素影响。综合考虑多方面因素 ,就有潜力设计出经济高效的土壤淋洗系统。土壤淋洗法有很多优点 ,尽管也存在一些问题 ,但其技术上的优势也是其他方法难以取代的 ,所以有良好的应用前景。     

Experimental investigation of pneumatic soil vapor extraction

Soil Vapor Extraction (SVE) is a common remediation technique for removing volatile organic compounds from unsaturated contaminated soils. Soil heterogeneities can however cause serious limitations to the applicability of SVE due to air bypassing low permeable areas of the soil, leading to diffusion limitation of the remediation. To enhance removal from areas subject to diffusion limitation a new remediation technique, pneumatic soil vapor extraction, is proposed. In contrast to traditional SVE, in which soil vapor is extracted continuously by a vacuum pump, pneumatic SVE is based on enforcing a sequence of large pressure drops on the system to enhance the recovery from the low-permeable areas. The pneumatic SVE technique was investigated in the laboratory using TCE as a model contaminant. 2D-laboratory tank experiments were performed on homogeneous and heterogeneous sand packs. The heterogeneous packs consisted of a fine sand lens surrounded by a coarser sand matrix. As expected when using traditional SVE, the removal of TCE from the low permeable lens was extremely slow and subject to diffusion limitation. In contrast when pneumatic venting was used removal rates increased by up to 77%. The enhanced removal was hypothesized to be attributed to mixing of the contaminated air inside the lens and generation of net advective transport out of the lens due to air expansion.     

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。     

Remediation of heavy metals contaminated soils by ball milling

In the present work, the use of ball milling reactors for the remediation of lead contaminated soils was investigated. Lead immobilization was achieved without the use of additional reactants but only through the exploitation of weak transformations induced on the treated soil by mechanical loads taking place during collisions among milling media. The degree of metal immobilization was evaluated by analyzing the leachable fraction of Pb(II) obtained through the "synthetic precipitation leaching procedure". The reduction of leachable Pb(II) from certain synthetic soils, i.e., bentonitic, sandy and kaolinitc ones, was obtained under specific milling regimes. For example, for the case of bentonitic soils characterized by a Pb(II) concentration in the solid phase equal to 954.4 mg kg(-1), leachable Pb(II) was reduced, after 7 h of mechanical treatment, from 1.3 mg l(-1) to a concentration lower than the USEPA regulatory threshold (i.e., 0.015 mg l(-1) for drinkable water). Similar results were obtained for sandy and kaolinitic soils. X-ray diffraction, scanning electron microscopy, electron dispersive spectroscopy and granulometric analyses revealed no significant alterations of the intrinsic character of sandy and bentonitic soils after milling except for a relatively small increase of particles size and a partial amorphization of the treated soil. On the other hand, the mechanical treatment caused the total amorphization of kaolinitic soil. The increase of immobilization efficiency can be probably ascribed to specific phenomena induced by mechanical treatment such as entrapment of Pb(II) into aggregates due to aggregation, solid diffusion of Pb(II) into crystalline reticulum of soil particles as well as the formation of new fresh surfaces (through particle breakage) onto which Pb(II) may be irreversibly adsorbed.     

Efficiency of surfactant-enhanced desorption for contaminated soils depending on the component characteristics of soil-surfactant--PAHs system

The sorption of surfactants onto soils has a significant effect on the performance of surfactant enhanced desorption. In this study, the efficiency of surfactants in enhancing desorption for polycyclic aromatic hydrocarbons (PAHs) contaminated soils relative to water was evaluated with a term of relative efficiency coefficient (REC). Since the sorption of surfactants onto soils, surfactants only enhanced PAH desorption when REC values were larger than 1 and the added surfactant concentration was greater than the corresponding critical enhance desorption concentration (CEDC), which was defined as the corresponding surfactant concentration with REC=1. A model was utilized to describe and predict the REC and CEDC values for PAH desorption. The model and experimental results indicated that the efficiency of surfactants in enhancing PAH desorption showed strong dependence on the soil composition, surfactant structure and PAH properties. These results are of practical interest for the selection of surfactant to optimize soil remediation technologies.