重金属污染土壤修复技术中有关淋洗剂的研究进展

淋洗法是修复污染土壤的一种很有效的方法 ,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。淋洗法就是使用淋洗剂来清洗土壤 ,使土壤中污染物随淋洗液流出 ,然后对淋洗液及土壤进行后续处理 ,从而达到修复污染土壤的目的。而淋洗剂的选择是影响这一技术效率高低的主要因素之一。本文对目前淋洗剂的应用情况 ,作用机制进行了总结和评价。探讨了天然有机酸、生物表面活性剂等对环境影响小的淋洗液的应用前景。并根据“以废治污”的指导思想提出并分析了以柠檬酸废水和味精废水作为淋洗剂修复重金属污染土壤的可行性。     

Microemulsion‐mediated removal of residual gasoline from soil columns

In situ pumping of micellular solutions of surfactant (S) and cosurfactant (CoS) in water (W) through contaminated soils or aquifers offers potential for enhanced remediation of residual nonaqueous‐phase liquids (NAPLs). Extremely low interfacial tension generated between a W/S/CoS mixture and residual NAPL in soil pores may initially mobilize the NAPL, which is then transported temporarily as a separate phase by immiscible displacement. The NAPL is then solubilized by micro‐emulsification as the W/S/CoS mixture forms a stable W/S/CoS/NAPL micro‐emulsion that undergoes miscible displacement through the pore space. This remediation technique was tested under laboratory conditions by sequentially flushing a saline solution and a W/S/CoS mixture through columns of a sandy soil recently contaminated with residual leaded gasoline (LG). Prior to the flushings, the soil was initially contaminated by applying a W/S/CoS/LG microemulsion. A simple conceptual transport model with kinetic clogging of soil pores adequately described breakthrough curves for gasoline and organolead in the soil columns.     

石油污染土壤植物-微生物修复研究进展

依据国内外近10年来有关石油污染土壤生物修复研究的成果,综合阐述了石油污染土壤的植物修复、微生物修复及植物-微生物联合修复方法研究,重点讨论植物-微生物联合作用,主要包括植物根际微生物、根分泌物以及菌根对石油污染物降解的影响,提出了污染土壤原位修复中需要重视的问题.     

我国污染土壤修复研究现状与展望

介绍了我国土壤污染的突出特点及其危害,回顾了污染土壤从清洁技术研究到物理、化学和生物修复研究的历程,总结了污染土壤修复取得的初步成果,提出了污染土壤修复的实质和系统技术方法。根据我国土壤污染的实际和修复需求,本文提出了当前本领域急需开展的研究内容,预测了污染土壤修复研究对环境科学相关学科的推动作用。     

Selection of a remediation scenario for a diesel-contaminated site using LCA

Goal and Scope A comparison of in situ and ex situ treatment scenarios for a diesel-contaminated site was performed using an evolutive LCA. Treatment time along with primary (residual contamination left in soil or groundwater after treatment) and secondary (impacts due to remediation) environmental impacts were considered. The site under study had a light Non Aqueous Phase Liquid (LNAPL) thickness of up to 1 m, a diesel soil concentration of 10,500 mg/kg and a residual contamination in groundwater. Methods Four treatment scenarios to remove LNAPL and to treat soil and groundwater were compared: 1) pump and treat 2) bioslurping, bioventing and biosparging 3) bioslurping, bioventing and chemical oxidation and 4) ex situ treatment using biopiles. The technologies’ design was performed using simulation tools and analytical equations. The LCA was evaluated for each year of treatment. Environmental impacts were assessed using the U.S. EPA Tool for the Reduction and Assessment of Chemical and Other Environmental Impacts (TRACI) method. Results and Discussion The biological in situ scenario (2) showed the least primary and secondary impacts but its treatment time was more than 4 times longer than that obtained for the ex situ scenario (4). The ex situ scenario showed the best treatment time but its secondary impacts were significantly higher than those found for the biological in situ scenario due to the pavement of the treatment area. The combined biological and chemical in situ scenario (3) was the worst in terms of secondary impacts while the pump and treat scenario (1) was the worst in terms of primary impacts. Two scenarios were selected: one based upon low environmental impacts and the other on the fastest treatment time. Conclusions Even without excavation, an in situ treatment can generate more secondary impacts than an ex situ treatment. Low environmental impact scenarios require time while rapid treatment scenarios generate high environmental impacts. The selection of the best remediation scenario will depend on the site owner’s priority. Recommendations Better characterization factors for aggregated substances are required. This paper is openly accessible!     

A feasibility study for the in situ remediation of a former tank farm

A feasibility study of the in situ remediation of a former tank farm (on a petrol station) was made over a period of 150 days at 10 °C. The natural attenuation (which is a sum of the abiotic losses and the natural biodegradation by the indigenous soil microorganisms) and the effect of biostimulation by inorganic nutrient supply were investigated. The contamination was not homogeneously distributed in the seven soil samples investigated. Nutrient addition had no statistically significant effect on hydrocarbon decontamination. A remarkable part of the decontamination had to be attributed to natural attenuation. Soil microbial counts and CO₂ evolution indicated a negative effect of nutrition on the number of microbial hydrocarbon degraders and on soil microbial activity.     

In situ bioremediation of hydrocarbon in soil

Laboratory and field experiments were carried out for bioremediation of soils contaminated by fuel oil and motor oil. Bioventing was combined with the application of selected bacteria and dissolved nutrients. In the field experiments, soil gas was evacuated by air pumps from the permeable boreholes. The process was followed by both soil and gas analysis. Biodegradation of oil contamination and the microbial activity was measured by the oil and cell concentration in the soil. In 2 months, the oil content decreased considerably, and the cell number increased by one order of magnitude or more. The evacuated gas was tested for CO₂, O₂ and volatilized hydrocarbon content. The CO₂ level proves the presence of biodegradation: a permanent high value about ten times higher than normal, could be measured for 2 months, followed by a slow decrease in the third month. Volatilized hydrocarbon content was the highest in the first 2 d. After a continuous decrease, it dropped under the threshold of measurability for the third month. Selective biodegradation of hydrocarbon mixtures (oily wastes) was investigated as well: gas Chromatographic oil analysis showed the changes in the oil composition. The appropriate microflora was working in an ideal commensalism, and as a result, all of the hydrocarbon components were degraded nearly to the same extent.     

Phytoextraction of Pb and Cu contaminated soil with maize and microencapsulated EDTA

Chelate-assisted phytoextraction using agricultural crops has been widely investigated as a remediation technique for soils contaminated with low mobility potentially toxic elements. Here, we report the use of a controlled-release microencapsulated EDTA (Cap-EDTA) by emulsion solvent evaporation to phytoremediate soil contaminated with Pb and Cu. Incubation experiments were carried out to assess the effect of Cap- and non-microencapsulated EDTA (Ncap-EDTA) on the mobility of soil metals. Results showed EDTA effectively increased the mobility of Pb and Cu in the soil solution and Cap-EDTA application provided lower and more constant water-soluble concentrations of Pb and Cu in comparison with. Phytotoxicity may be alleviated and plant uptake of Pb and Cu may be increased after the incorporation of Cap-EDTA. In addition phytoextraction efficiencies of maize after Cap- and Ncap-EDTA application were tested in a pot experiment. Maize shoot concentrations of Pb and Cu were lower with Cap-EDTA application than with Ncap-EDTA. However, shoot dry weight was significantly higher with Cap-EDTA application. Consequently, the Pb and Cu phytoextraction potential of maize significantly increased with Cap-EDTA application compared with the control and Ncap-EDTA application.     

Phytoremediation of arsenic and lead in contaminated soil using Chinese brake ferns (Pteris vittata) and Indian mustard (Brassica juncea)

Field and greenhouse experiments were performed to assess the performance of phytoremediation of arsenic and lead from contaminated soil at an EPA Superfund site (Barber Orchard). Chinese Brake ferns (Pteris vittata) were used to extract arsenic. On average, fern shoot arsenic concentrations were as high as 20 times the soil arsenic concentrations under field conditions. It was estimated that 8 years would be required to reduce the acid-extractable portion of soil arsenic to safe levels (40 mg/kg). The effect of soil pH on arsenic extraction was also investigated. Results indicate that increasing soil pH may improve arsenic removal. Indian mustard plants (Brassica juncea) were used under greenhouse conditions to phytoextract soil lead. EDTA was applied to soil and was found to improve lead extraction. When the EDTA concentration was 10 mmol EDTA/kg soil in soil containing 338 mg Pb/kg soil, mustard plants extracted approximately 32 mg of lead. In conclusion, phytoremediation would be a suitable alternative to conventional remediation techniques, especially for soils that do not require immediate remediation.     

The interactions of composting and biochar and their implications for soil amendment and pollution remediation: a review

Compost and biochar, used for the remediation of soil, are seen as attractive waste management options for the increasing volume of organic wastes being produced. This paper reviews the interaction of biochar and composting and its implication for soil amendment and pollution remediation. The interaction of biochar and composting affect each other’s properties. Biochar could change the physico-chemical properties, microorganisms, degradation, humification and gas emission of composting, such as the increase of nutrients, cation exchange capacity (CEC), organic matter and microbial activities. The composting could also change the physico-chemical properties and facial functional groups of biochar, such as the improvement of nutrients, CEC, functional groups and organic matter. These changes would potentially improve the efficiency of the biochar and composting for soil amendment and pollution remediation. Based on the above review, this paper also discusses the future research required in this field.     

Addition of allochthonous fungi to a historically contaminated soil affects both remediation efficiency and bacterial diversity

Botryosphaeria rhodina DABAC P82 and Pleurotus pulmonarius CBS 664.97 were tested for their ability to grow and to degrade aromatic hydrocarbons in an aged contaminated soil. To evaluate the impact of indigenous microflora on the overall process, incubations were performed on both fumigated and nonfumigated soils. Fungal colonization by B. rhodina was unexpectedly lower in the fumigated than in the nonfumigated soil while the growth of P. pulmonarius showed an opposite response. Degradation performances and detoxification by both fungi in the nonfumigated soil were markedly higher than those observed in the fumigated one. Heterotrophic bacterial counts in nonfumigated soil augmented with either B. rhodina or P. pulmonarius were significantly higher than those of the corresponding incubation control (6.7 ± 0.3 × 10⁸ and 8.35 ± 0.6 × 10⁸, respectively, vs 9.2 ± 0.3 × 10⁷). Bacterial communities of both incubation controls and fungal-augmented soil were compared by numerical analysis of denaturing gradient gel electrophoresis profiles of polymerase chain reaction (PCR)-amplified 16S ribosomal RNA (rRNA) genes and cloning and sequencing of PCR-amplified 16S rRNA genes. Besides increasing overall diversity, fungal augmentation led to considerable qualitative differences with respect to the pristine soil.     

Fenton's Reagent-Based In Situ Chemical Oxidation Treatment of Saturated and Unsaturated Soils at a Historic Railroad Site

A targeted treatment program utilizing in situ chemical oxidation was used to remediate diesel fuel-derived petroleum compounds in unsaturated and saturated soils at a historic railroad facility. This program consisted of multiple injections at varying depths within temporary Geoprobe® injection points. The actual treatment time was less than 3 months. Overall concentrations of volatile and semivolatile organic petroleum compounds were reduced by approximately 70%, while the total petroleum hydrocarbon concentration was reduced by nearly 50%. Treatment efficiency in unsaturated soil was similar to that in saturated soil. The results of the remedial program indicate that the effect of grain size of the subsurface materials on treatment efficacy is significant. The project has shown that the use of this technology can be as effective as other in situ treatment technologies used for treating subsurface diesel fuel contamination.     

Influence of Bentonite Proportion in Natural Clay on Pb2+ ions Sorption: Response Surface Methodology,Kinetics and Equilibrium Studies

The influence of natural clay's bentonite proportion on Pb²⁺ sorption capacity was investigated using response surface methodology (RSM), kinetics and equilibrium studies. Experiments were conducted at different initial pH (3–7), bentonite to clay ratio (0–100%), initial Pb²⁺ ions concentration (20–120 mg/L) and sorbent dosage (0.2–1 g). Under the RSM study, data obtained from 27 experiments undertaken were found to fitted second-order polynomial model (R² = 0.998 and R²-predicted = 0.994). Analysis of variance showed that the Pb²⁺ sorption capacity was influenced according to the order; initial concentration> mass of adsorbent > initial pH > bentonite proportion. Optimal operating conditions were obtained at initial pH 5, 0.2 g sorbent dosage, 30% bentonite to clay ratio and 100 mg/L Pb²⁺ ion concentration. Regardless of the bentonite proportion, Pb²⁺ sorption kinetics followed pseudo-second-order associated with intra-particle diffusion. The sorption isotherm for the clay which was described by Freundlich yielded higher adsorption capacity (25 mg/g) while that of the bentonite was described by Langmuir model with lower maximum sorption capacity of 15 mg/g. These results suggest that sorption of the Pb²⁺ ions was not likely to significantly impact on the removal of Pb²⁺ ions during electrokinetic remediation process of clay having different proportion of bentonite.     

Feasibility of in situ implementation of vibrations to mobilize NAPL ganglia

A growing number of incidents of nonaqueous phase liquid (NAPL) spills in the recent past have warranted development of innovative and cost‐effective remediation technologies. Of particular concern is the entrapment of LNAPL (NAPL lighter than water) in the form of ganglia or blobs near the water table by virtue of strong capillary forces. The residual ganglia are the leftover component after pumping of free product and typically occupy 20 to 60% of the pore space. Mobilization of these ganglia would require unrealistically high hydraulic gradients and is often beyond the scope of pump‐and‐treat processes. This paper deals with the feasibility of in situ implementation of localized vibrations for controlled mobilization and collection of LNAPL ganglia. Specifically, the paper covers three components. First, the principles involved in soil‐water‐NAPL interactions under the influence of vibrations are discussed. The effects of vibrations on a soil‐NAPL‐water medium are postulated in terms of pore structure and relative density changes, changes in the permeability of the medium as a result of the changes in pore structure, and development of cyclic pore pressures. Second, results from bench‐scale experiments are presented that involved vibrating contaminated soils under the simultaneous influence of hydraulic gradients. A bench‐scale model consisting of a vibrator integrated with an injection and pumping system was found to be successful in these experiments. The results from the tests showed that up to 85% removal of ganglia can be achieved using this process. Third, the principles involved in the vibratory mobilization were applied to in situ conditions to develop a methodology to estimate the zone of influence of the process. The analogy between this process and an existing geotechnical process known as vibroflotation is exploited to demonstrate the methodology.     

Organic acid enhanced soil risk element (Cd, Pb and Zn) leaching and secondary bioconcentration in water lettuce (Pistia stratiotes L.) in the rhizofiltration process

The use of natural chelates to enhance risk element mobility combined with rhizofiltration by free floating macrophytes have not been thoroughly studied in recent years. The aim of this study was to investigate the efficiency of organic acids in soil by conducting flushing experiments to enhance the mobility of Cd, Pb, and Zn from soil to solution. In addition, the bioaccumulation of Cd, Pb, and Zn, in water lettuce (Pistia stratiotes L.) will be studied as they affect the biomass in the rhizofiltration process. The results revealed that citric and tartaric acids mobilised the highest amount of all risk elements. In comparison to control, citric acid mobilised 71%, 181%, and 112% of Cd, Pb, and Zn while tartaric acid mobilised 70%, 155%, and 135% of Cd, Pb, and Zn respectively. The bioconcentration factor was approximately 2-5 times higher for juvenile plants than mature plants for all treatments as well as for both parts (leaves and roots). The risk element translocation into aerial parts decreased with increased time. Juvenile and mature plants proved a high accumulation potential and a 3 week growth period was observed as a sufficient time period to remove more than 80% of Cd, Pb, and Zn.     

Methodology for using contaminated soil leachability testing to determine soil cleanup levels at contaminated petroleum underground storage tank (UST) sites

The costs of environmental remediation at leaking petroleum underground storage tank (UST) sites are influenced significantly by soil cleanup levels. The use of conservative generic soil cleanup levels may be inappropriate at some sites contaminated by leaking petroleum USTs. At many contaminated sites, a primary objective of site remediation is long‐term protection of water resources (e.g., groundwater) from pollution. Leaching of pollutants from residual soil contamination to groundwater is a primary consideration in establishing site‐specific soil cleanup levels at fuel‐contaminated sites. The use of laboratory soil leachability testing methods may be useful in objectively evaluating the leaching potential of contaminants from residual soil contamination and estimating potential groundwater impacts. Developing soil cleanup levels that are protective of water resources must include a technically sound integration of site‐specific soil leachability data and contaminant attenuation factors. Evaluation of the leaching potentials of soil contaminants may also provide essential supplementary information for other site characterization methods that may be used to evaluate risks to human health. Contaminant leachability testing of soils may provide a cost‐effective and technically based method for determining soil cleanup levels that are protective of groundwater resources at contaminated petroleum UST sites.     

Oxalate Extraction of Pb and Zn from Polluted Soils: Solubility Limitations

Oxalate (Ox) was used to extract Pb and Zn from industrially contaminated soils. Although Ox effectively releases metals bound by hydrous oxide soil components, it forms insoluble salts with some heavy metals unlike conventional extractants (e.g., EDTA). The insolubility of PbOx(s) (K_sp=2.74 × 10^?11) precluded the use of Ox as a single-step extractant even for soils mildly contaminated with Pb. The usefulness of Ox as a Zn extractant, however, depends on the level of soil contamination. A Zn solubility model, based on published equilibrium constants, was developed to assess Ox suitability as a function of system conditions. Precipitation of ZnOx(s) hindered Zn recovery under acidic conditions where formation of soluble oxalato complexes was small. For pH<3, the presence of 1?M Ox actually reduced Zn release compared to simple acid washing. Although Ox displaces oxide-bound metals and thus is potentially useful in soil washing, solubility limitations must be defined for effective remediation of metal-laden soils.     

Impact of Humin on Soil Adsorption and Remediation of Cd(II), Pb(II), and Cu(II)

In situ immobilization constitutes a promising technology for the mitigation of contaminants, through the reduction of metal bioavailability and mobility. This study investigated the adsorption isotherms and kinetic characteristics of humin extracted from peat soils. We also studied the influences of the pH, ionic strengths, and soluble organic matter concentrations of soil solutions on the adsorptive properties of humin, and compared its ability to detoxify potentially toxic metals in both actual and simulated soil solutions. The study results indicated that humin contains a massive population of oxygen-containing functional groups. Its adsorption capacity for Pb(II) was greater than that for Cu(II), which exceeded that for Cd(II). The adsorption of humin for Pb(II) conformed to the Freundlich model, while the adsorption of humin for Cd(II) and Cu(II) followed the Langmuir model. The adsorption kinetics of humin with respect to potentially toxic metals aligned well with second-order kinetics equations. As the pH was elevated, the potentially toxic metal adsorption by humin increased rapidly. Electrolyte ions and tartaric acids in solution both inhibited the adsorption of potentially toxic metals by humin, and its ability to inactivate potentially toxic metals. This was shown to be improved in actual field soil solutions in contrast to simulated soil solutions.     

Lead Distribution and Mobility in a Soil Embankment Used as a Bullet Stop at a Shooting Range

The distribution of lead in and below a soil embankment used as a stop butt for lead bullets at a sport shooting range for more than 30 years was investigated. A vertical profile, just behind the shooting target, was mapped by 54 soil samples characterized by contents of lead bullets, soil lead, and easily leachable lead as measured in a leaching test (L/S 2). At the target, the soil contained up to 40% metallic lead and 5 to 10% lead associated with the soil particles (<2?mm). The leaching test showed concentrations of dissolved lead in the range 5 to 20?mg/l. However, in the bottom of the stop butt (about 1?m lower than the target) soil lead was only slightly elevated, and no increase in lead was found below the stop butt in the original soil profile. In the lower part of the stop butt, pH was around 5, which is considered to favor lead migration, but in the soil samples with lead bullets present pH was between 6 and 7. The elevated pH values, probably caused by the corrosion of lead bullets, may have been a significant factor in limiting the migration of lead in the stop butt. The investigation showed that the lead in the stop butt did not affect the surroundings, but that the high lead content of the soil would require that this be treated as waste if the facility was abandoned.