Remediation of DDTs contaminated soil in a novel Fenton-like system with zero-valent iron

Application of a novel Fenton-like system with zero-valent iron, EDTA and Air (ZVI/EDTA/Air) was investigated to degrade dichlorodiphenyltrichloroethane (DDT), dichlorodiphenyldichloroethane, and dichlorodiphenyldichloroethylene (DDE) in the actual contaminated soil from an organochlorine pesticide site. It was found DDTs in the soil were effectively degraded by the system at room temperature, ambient atmosphere pressure and near neutral pH. The dosages of EDTA and ZVI were the dominant factors influencing the removal of contaminants. An increase of EDTA from 0.05 to 0.2 mM and ZVI from 1 to 5 g L^?1 improved the removal of the contaminants significantly. However, excessive amount of EDTA led to a negative effect on the degradation process. Meanwhile, EDTA was simultaneously degraded so as to avoid the secondary pollution risk on soil remediation. Only a small amount of 4,4′-DDE and 2,2-bis(4-chlorophenyl)-1-chloroethylene (4,4′-DDMU) generated as the intermediates of DDT degradation during the process. Our investigation suggests that the Fenton-like system is a promising alternative for remediation of organochlorine pesticides contaminated soils.     

污染土壤修复效果评定方法的研究

在实施污染土壤修复的环境工程后,需要通过灵敏和有效的评定方法对污染土壤修复的效果进行评定.然而,单纯依靠化学方法进行污染土壤修复效果的评定,不能揭示土壤的整体质量特征,因此需要生态毒理方法作为相互补充的手段.本文概述了植物毒性评定法、陆生无脊椎动物评定法和土壤微生物评定法及其在污染土壤修复效果评定中的应用,并对污染土壤修复效果评定方法的发展前景进行展望.     

Detailed characterization of polar compounds of residual oil in contaminated soil revealed by Fourier transform ion cyclotron resonance mass spectrometry

Effects of remediation technologies on polar compounds of crude oil in contaminated soils have not been well understood when compared to hydrocarbons. In this study, ultrahigh resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) was used to characterize the changes in NSO polar compounds of crude oil and residual oil after long-term natural attenuation, biostimulation and subsequent ozonation following biostimulation of contaminated soils. N₁ and O₁ species, which were abundant in the crude oil, were selectively biodegraded, and species with higher double bond equivalent values and smaller carbon numbers appeared to be more resistant to microbial alteration. O₂-O₆ species were enriched by biodegradation and contained a large number of compounds with a high degree of unsaturation. Ozone could react with a variety of polar compounds in residual oil after biodegradation and showed high reactivity with polar species containing aromatic or multi-aliphatic rings, including the residual N₁ and O₁ species, naphthenic acids and unsaturated O₃-O₆ compounds. Fatty acids and O₃-O₈ species dominated by saturated alkyl compounds were resistant to ozonation or the primarily incomplete ozonation products. Principal component analysis of identified peaks in the FT-ICR MS spectra provided a comprehensive overview of the complex samples at the molecular level and the results were consistent with the detailed analysis. Taken together, these results showed the high complexity of polar compounds in residual oils after biodegradation or ozonation in contaminated soil and would contribute to a better understanding of bioremediation and ozonation processes.     

Slurry-phase ozonation for remediation of sediments contaminated by polycyclic aromatic hydrocarbons

Polycyclic aromatic hydrocarbons (PAHs) are a group of toxic, persistent, bioaccumulating organic compounds containing two or more fused aromatic rings. They are listed by the U.S. Environmental Protection Agency as priority pollutants because of their carcinogenicity and toxicity. Employing ozonation as a remediation technique, this work investigated the treatability of a sediment sample from a freshwater boat slip subjected to coal tar contamination over a long period. The contaminated sediment sample contained high levels of PAHs in the forms of naphthalene, phenanthrene, pyrene, and benzo[a]pyrene, among other byproducts present in the humic and solid phases of the sediment. The objectives of this work were to examine (1) the degradation of PAHs in the contaminated sediment as treated by ozonation in the slurry form, (2) the effects of ozonation upon the soil matrix and the biodegradability of the resultant PAH intermediates, and (3) the feasibility of a combined technique using O3 as a pretreatment followed by biological degradation. The sediment was made into 3% w/w soil slurries and ozonated in a 1.7-L semi-batch, well-stirred reactor equipped with pH control and a cold trap for the gaseous effluent. Samples were collected after different ozonation durations and tested for biochemical oxygen demand (BOD), chemical oxygen demand (COD), UV absorbance, and toxicity, along with quantitative and qualitative determinations of the parent and daughter intermediates using gas chromatography/flame ionization detection (GC/FID), GC/mass spectrometry (MS), and ion chromatography (IC) techniques. The GC/MS technique identified 16 compounds associated with the humic and solid phases of the sediment. Intermediates identified at different ozonation times suggested that the degradation of PAHs was initiated by an O3 attack resulting in ring cleavage, followed by the intermediates' oxidation reactions with O3 and the concomitant OH radical toward their mineralization. Results suggested that ozonation for 2 hr removed 50-100% of various PAHs in the solid and liquid phases (as well as the aqueous and gaseous media resulting from the treatment process) of the sediment sample and that organic and inorganic constituents of the sediment were also altered by ozonation. Measurements and comparisons of BOD, COD, UV absorbance, and toxicity of the samples further suggested that ozonation improved the bioavailability and biodegradability of the contaminants, despite the increased toxicity of the treatment effluent. An integrated chemical-biological system appeared to be feasible for treating recalcitrant compounds.     

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.     

Fenton based remediation of polycyclic aromatic hydrocarbons-contaminated soils

This paper aims to review the applications of Fenton based treatments specifically for polycyclic aromatic hydrocarbons-contaminated soils. An overview of the background and principles of Fenton treatment catalysed by both homogenous (conventional and modified Fenton) and heterogeneous (Fenton-like) catalysts is firstly presented. Laboratory and field soil remediation studies are then discussed in terms of efficiency, kinetics and associated factors. Four main scopes of integrated Fenton treatments, i.e. physical-Fenton, biological-Fenton, electro-Fenton and photo-Fenton are also reviewed in this paper. For each of these integrated remediation technologies, the theoretical background and mechanisms are detailed alongside with achievable removal efficiencies for polycyclic aromatic hydrocarbons in contaminated soils compared to sole Fenton treatment. Finally, the environmental impacts of Fenton based soil treatments are documented and discussed.     

Removal of sorbed polycyclic aromatic hydrocarbons from soil, sludge and sediment samples using the Fenton's reagent process

The use of the Fenton's reagent process has been investigated for the remediation of environmental matrices contaminated by polycyclic aromatic hydrocarbons (PAHs). Laboratory experiments were first conducted in aqueous solutions, to study the kinetics of oxidation and adsorption of PAHs. Benzo[a]pyrene was more rapidly degraded than adsorbed, while only partial oxidation of fluoranthene occurred. In the case of benzo[b]fluoranthene, its adsorption prevented its oxidation. Besides competition effects between PAHs were found, with slower oxidation of mixtures as compared to single PAH solutions. Apparition of some by-products was observed, and a di-hydroxylated derivative of benzo[a]pyrene could be identified under our conditions. Consequently, application to solid environmental matrices (soil, sludge and sediment samples) was performed using large amounts of reagents. The efficiency of the Fenton treatment was dependent on the matrix characteristics (such as its organic carbon content) and the PAH availability (correlated to the date and level of contamination). However, no pH adjustment was required, as well as no iron addition due to the presence of iron oxides in the solid matrices, suggesting the potential application of Fenton-like treatment for the remediation of PAH-contaminated environmental solids.     

Effects of remediation train sequence on decontamination of heavy metal-contaminated soil containing mercury

When a contaminated site contains pollutants including both nonvolatile metals and Hg, one single remediation technology may not satisfactorily remove all contaminants. Therefore, in this study, chemical extraction and thermal treatment were combined as a remediation train to remove heavy metals, including Hg, from contaminated soil. A 0.2 M solution of ethylenediamine tetraacetic acid (EDTA) was shown to be the most effective reagent for extraction of considerable amounts of Cu, Pb, and Zn (>50%). Hg removal was ineffective using 0.2 M EDTA, but thermogravimetric analysis suggested that heating to 550°C with a heating rate of 5°C/min for a duration of 1 hr appeared to be an effective approach for Hg removal. With the employment of thermal treatment, up to 99% of Hg could be removed. However, executing thermal treatment prior to chemical extraction reduced the effectiveness of the subsequent EDTA extraction because nonvolatile heavy metals were immobilized in soil aggregates after the 550°C treatment. The remediation train of chemical extraction followed by thermal treatment appears to remediate soils that have been contaminated by many nonvolatile heavy metals and Hg.

ImplicationsA remediation train conjoining two or more techniques has been initialized to remove multiple metals. Better understandings of the impacts of treatment sequences, namely, which technique should be employed first on the soil properties and the decontamination efficiency, are in high demand. This study provides a strategy to remove multiple heavy metals including Hg from a contaminated soil. The interactions between thermal treatment and chemical extraction on repartitioning of heavy metals was revealed. The obtained results could offer an integrating strategy to remediate the soil contaminated with both heavy metals and volatile contaminants.     

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。     

Polychlorinated biphenyls-containing electrical insulating oil contaminated soil treatment with calcium and magnesium peroxides

Calcium and magnesium peroxides were applied for the treatment of soil contaminated by polychlorinated biphenyls-containing electrical insulating oil (Aroclor 1016). The removal of PCB-containing electrical insulating oil was achieved with the addition of either calcium peroxide or magnesium peroxide alone and dependent on dosages of the chemical. A 21-d treatment of 60% watered soil with the moderate addition (chemical/oil weight ratio of 0.005/1) of either calcium peroxide or magnesium peroxide resulted in nearly complete (96 ± 2%) oil removal, unsubstantial increase in soil pH and almost no changes in oxygen consumption and dehydrogenase activity, making it suitable for the soil decontamination.     

Physicochemical and biological quality of soil in hexavalent chromium-contaminated soils as affected by chemical and microbial remediation

Chemical and microbial methods are the main remediation technologies for chromium-contaminated soil. These technologies have progressed rapidly in recent years; however, there is still a lack of methods for evaluating the chemical and biological quality of soil after different remediation technologies have been applied. In this paper, microbial remediation with indigenous bacteria and chemical remediation with ferrous sulphate were used for the remediation of soils contaminated with Cr(VI) at two levels (80 and 1,276 mg kg^?1) through a column leaching experiment. After microbial remediation with indigenous bacteria, the average concentration of water-soluble Cr(VI) in the soils was reduced to less than 5.0 mg kg^?1. Soil quality was evaluated based on 11 soil properties and the fuzzy comprehensive assessment method, including fuzzy mathematics and correlative analysis. The chemical fertility quality index was improved by one grade using microbial remediation with indigenous bacteria, and the biological fertility quality index increased by at least a factor of 6. Chemical remediation with ferrous sulphate, however, resulted in lower levels of available phosphorus, dehydrogenase, catalase and polyphenol oxidase. The result showed that microbial remediation with indigenous bacteria was more effective for remedying Cr(VI)-contaminated soils with high pH value than chemical remediation with ferrous sulphate. In addition, the fuzzy comprehensive evaluation method was proven to be a useful tool for monitoring the quality change in chromium-contaminated soils.     

Remediation of phenanthrene-contaminated soil by simultaneous persulfate chemical oxidation and biodegradation processes

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous compounds with carcinogenic and/or mutagenic potential. To address the limitations of individual remediation techniques and to achieve better PAH removal efficiencies, the combination of chemical and biological treatments can be used. The degradation of phenanthrene (chosen as a model of PAH) by persulfate in freshly contaminated soil microcosms was studied to assess its impact on the biodegradation process and on soil properties. Soil microcosms contaminated with 140 mg/kg_{DRY SOIL} of phenanthrene were treated with different persulfate (PS) concentrations 0.86–41.7 g/kg_{DRY SOIL} and incubated for 28 days. Analyses of phenanthrene and persulfate concentrations and soil pH were performed. Cultivable heterotrophic bacterial count was carried out after 28 days of treatment. Genetic diversity analysis of the soil microcosm bacterial community was performed by PCR amplification of bacterial 16S rDNA fragments followed by denaturing gradient gel electrophoresis (DGGE). The addition of PS in low concentrations could be an interesting biostimulatory strategy that managed to shorten the lag phase of the phenanthrene biological elimination, without negative effects on the physicochemical and biological soil properties, improving the remediation treatment.     

污染土壤修复效果评定方法的研究

在实施污染土壤修复的环境工程后，需要通过灵敏和有效的评定方法对污染土壤修复的效果进行评定。然而，单纯依靠化学方法进行污染土壤修复效果的评定，不能揭示土壤的整体质量特征，因此需要生态毒理方法作为相互补充的手段。本文概述了植物毒性评定法、陆生无脊椎动物评定法和土壤微生物评定法及其在污染土壤修复效果评定中的应用，并对污染土壤修复效果评定方法的发展前景进行展望。     

Efficacy of in-situ for the remediation of PAH contaminated soils

Polycyclic aromatic hydrocarbons (PAHs) are of environmental concern because many PAHs are either carcinogens or potential carcinogens. Petroleum products are a major source of PAHs. The occurrence of PAH contamination is widespread and novel treatment technologies for the remediation of contaminated soils are necessary.Ozone has been found to be extremely useful for the degradation of PAHs in soils. For these compounds, the reaction with molecular ozone appears to be the more important degradation pathway. Greater than 95% removal of phenanthrene was achieved with an ozonation time of 2.3 h at an ozone flux of 250 mg h⁻¹. After 4.0 h of treatment at an ozone flux of 600 mg h⁻¹, 91 % of the pyrene was removed. We have also found that the more hydrophobic PAHs (e.g. chrysene) react more slowly than would be expected on the basis of their reactivity with ozone, suggesting that partitioning of the contaminant into soil organic matter may reduce the reactivity of the compound. Even so, after 4 h of exposure to ozone, the chrysene concentration in a contaminated Metea soil was reduced from 100 to 50 mg kg⁻¹ .Ozone has been found to be readily transported through columns packed with a number of geological materials, including Ottawa sand, Metea soil, Borden aquifer material and Wurtsmith aquifer material. All of these geological materials exerted a limited (finite) ozone demand, i.e. the rate of ozone degradation in soil columns is very slow after the ozone demand is met. Moisture content was found to increase the ozone demand, most likely owing to the dissolution of gaseous ozone into the pore water. As once the initial ozone demand is met, little degradation of ozone is observed, it should be possible to achieve ozone penetration to a considerable distance away from the injection well, suggesting that in-situ ozonation is a feasible means of treating uncontaminated unsaturated soils. This is substantiated by two field studies where in-situ ozonation was apparently successful at remediating the sites.     

Study on the possibility of hydrogen peroxide pretreatment and plant system to remediate soil pollution

Hydrogen peroxide was widely selected as the chemical oxidant in chemical remediation or as the donor of oxygen in in situ aerobic bioremediation of organic pollutants. In this paper, hydrogen peroxide pretreatment and plant system was done to examine its possibility to remediate the heavy metal contaminated soil or heavy metal-organic combined contaminated soil. Heavy metal contaminated soil was collected from the heavily industrialized area, in Fuyang county, Zhejiang province, China. And heavy metal-organic combined contaminated soil was prepared from the same contaminated soil by spiking 100 microg g(-1) 2,4-dichlorophenol (2,4-DCP). Results showed that H2O2 could improve the dissipation of 2,4-DCP and enhance the availability of Cu and Zn in soil. The greatly increased DOC (dissolved organic carbon) in the oxidation process was probably the main reason for the greatly increased water soluble Cu in higher pH condition. Water soluble Zn, however, easily rebound to soil components with the time being and had no positive relation with dissolved organic carbon. Planting with ryegrass influenced the behavior of pollutants in soil. It was observed that the dissipation of 2,4-DCP could be enhanced by the presence of plant roots and the availability of Cu and Zn in the planted soil was changed due to the mobilization and rebound mechanisms in the rhizosphere. Co-contamination of 2,4-DCP caused the greater availability of Cu and Zn in H2O2 pretreatment. But with the ryegrass planting, it was easier to rebound to the less available phase in the rhizosphere. Both Cu and Zn concentration in shoots increased with the H2O2 treatment. Therefore our results suggested that H2O2 pretreatment was probably a promising way for promoting the dissipation of persistent organic pollutants and enhancing the solubility of Cu and Zn in soil. A combination of H2O2 pretreatment and suitable plant might be an efficient alternative for remedying heavy metal or heavy metal-organic contaminated soil.     

超声波净化石油污染土壤实验研究

为研究超声波技术处理石油污染土壤的影响因素,选取了土壤含油量、土水比、土壤类型、超声处理时间和超声功率5个因素进行了具有交互作用的正交实验,并讨论了各因素对土壤中石油污染物清除率的影响。实验结果表明超声波对土壤中石油污染物的净化效果明显,总石油烃(TPH)的清除率在23.0%到77.3%之间,土壤类型对净化效果的影响最为显著,粘土中的TPH清除率显著低于砂土。由超声空化引起的解吸作用和真空抽滤是实验过程中土壤TPH减少的主要途径。研究结果表明超声波技术用于石油污染土壤修复是可行并且有效果的。     

原位化学氧化法在土壤和地下水修复中的研究进展

综述了原位化学氧化法修复污染土壤及地下水的最新进展 ,着重介绍了几种氧化剂 ,如二氧化氯、双氧水及Fenton试剂、高锰酸钾和臭氧在土壤修复中的应用、不足及改进 ,并对化学氧化修复技术的发展前景进行了展望     

污染土壤化学修复技术研究与进展

污染土壤修复环境工程近年来发展迅猛,欧美等发达国家在其技术创新和设备改进2个层面都取得了长足进展。本文概述了化学淋洗修复技术(原位化学修复技术和异位化学修复技术)、化学还原与还原脱氯修复技术、化学氧化修复技术、溶剂浸提技术和土壤性能化学改良修复技术等污染土壤的化学修复技术原理、进展与适用性以及有关关键技术参数,并对其发展前景进行了展望。     

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.     

Kinetics of soil ozonation: an experimental and numerical investigation

This study investigates the use of ozone for soil remediation. Batch experiments, in which ozone-containing gas was continuously recycled through a soil bed, were conducted to quantify the rate of ozone self-decomposition and the rates of ozone interaction with soil organic and inorganic matter. Column experiments were conducted to measure ozone breakthrough from a soil column. Parameters such as ozone flow rate, soil mass, and ozonation time were varied in these experiments. After ozone concentration had reached steady state, the total organic carbon concentration was measured for all soil samples. The ozonation efficiency, represented by the ratio of soil organic matter consumed to the total ozone input, was quantified for each experiment. Numerical simulations were conducted to simulate experimentally obtained column breakthrough curves. Experimentally obtained kinetic rate constants were used in these simulations, and the results were in good agreement with experimental data. In contrast to previous studies in which soil inorganic matter was completely ignored, our experiments indicate that soil inorganic matter may also promote depletion of ozone, thus reducing the overall ozonation efficiency. Three-dimensional numerical simulations were conducted to predict the efficacy of ozonation for soil remediation in the field. These simulations indicate that such ozonation can be very effective, provided that effective circulation of ozone is achieved through appropriately placed wells.