Using Nanoscale Zero-Valent Iron for the Remediation of Polycyclic Aromatic Hydrocarbons Contaminated Soil

Abstract

The sites contaminated with recalcitrant organic compounds, such as polycyclic aromatic hydrocarbons (PAHs) with multiple benzene rings, are colossal and ubiquitous environmental problems. They are relatively nonbiodegradable and mutagenic, and 16 of them are listed in the U.S. Environment Protection Agency priority pollutants. Thus, the efficient and emerging remediation technologies for removal of PAHs in contaminated sites have to be uncovered urgently. In this decade, the zero-valent iron (ZVI) particles have been used successfully in the laboratory, pilot, and field, such as degradation of chlorinated hydrocarbons and remediation of the other pollutants. Nevertheless, as far as we know, little research has investigated for soil remediation; this study used nanoscale ZVI particles to remove pyrene in the soil. The experimental variables were determined, including reaction time, iron particle size, and dosage. From the results, both the micro- and nanoscales of ZVI were capable of removing the target compound in soil, but the higher removal efficiencies were by nanoscale ZVI because of the massive specific surface area. The optimal operating conditions to attain the best removal efficiency of pyrene were obtained while adding nanoscale ZVI 0.1 g/g soil within 60 min and 150 rpm of mixing. Thus, nanoscale ZVI has proved to be a promising remedy for PAH-contaminated soil in this study, as well as an optimistically predictable application for additional pilot and field studies.     

生物泥浆体系修复氯酚污染的土壤

利用生物泥浆体系研究了受氯酚污染土壤的修复特性。结果表明，对4-氯酚污染浓度为300mg／kg的土壤，土著微生物基本没有降解活性；投加高效菌可大大加快4-氯酚的降解进程。生物泥浆体系修复氯酚污染土壤的最佳工艺参数为：温度35℃，水土比3：1，投菌量5％。外加碳源和氮源可明显促进4-氯酚的降解，但外加磷源对降解的影响并不显著。     

Remediation of DDT-Contaminated Water and Soil by Using Pretreated Iron Byproducts from the Automotive Industry

The objective of this study was to quantify the effectiveness of different pretreated iron byproducts from the automotive industry to degrade DDT [(1,1,1-trichloro-2,2-bis(4-chlorophenyl) ethane] in aqueous solutions and soil slurry. Iron byproducts from automotive manufacturing were pretreated by three different methods (heating, solvent and 0.5N HCl acid washing) prior to experimentation. All pretreated irons were used at 5% (wt v^{? 1}) to treat 0.014 mM (5 mgL^{? 1}) of DDT in aqueous solution. Among the pretreated irons, acid pretreated iron results in the fastest destruction rates, with a pseudo first-order degradation rate of 0.364 d^{? 1}. By lowering the pH of the DDT aqueous solution from 9 to 3, destruction kinetic rates increase more than 20%. In addition, when DDT-contaminated soil slurry (3.54 mg kg^{? 1}) was incubated with 5% (wt v^{? 1}) acid-pretreated iron, more than 90% destruction of DDT was observed within 8 weeks. Moreover, DDT destruction kinetics were enhanced when Fe(II), Fe(III) or Al(III) sulfate salts were added to the soil slurry, with the following order of destruction kinetics: Al(III) sulfate > Fe(III) sulfate > Fe(II) sulfate. These results provide proof-of concept that inexpensive iron byproducts of the automotive industry can be used to remediate DDT-contaminated water and soil.     

污染土壤电动修复及供能方式研究进展

污染土壤电动修复是一项新兴的绿色原位修复技术.其原理是在土壤上施加直流电场,利用电迁移和电渗流去除污染物.电动修复的效率主要受到土壤pH、Zeta电位以及土壤化学性质等因素影响.在研究中使用的供能方式有两种控制电位法和控制电流法.这两种供能方式有不同特点和应用范围.控制电压法在理论模型、酸碱增强法以及阳离子膜增强修复方面有着广泛应用;控制电流法在计算目标污染物的迁移数、电渗析修复法以及难溶性重金属污染物的修复中得到应用.     

污染土壤的电动力学修复-Lasagna技术

介绍了Lasagna技术的原理和特点,以及目前所存在的问题.并对Lasagna技术的应用前景作了展望.     

电阻加热修复佳乐麝香污染土壤的工艺优化

佳乐麝香(Galaxolide,HHCB)是土壤中的一种新兴的半挥发性有机污染物,具有较高的毒性,需修复治理。电阻加热技术(electrical resistance heating,ERH)因加热均匀、效果好,逐渐被应用于有机污染土壤修复工程。采用自主研制的电阻加热装置,研究了加热过程中电场强度、土壤含水率和土壤粒径等因素对土壤HHCB去除效果的影响,并采用响应面法对工艺参数进行了优化。结果表明,土壤 HHCB去除率随电场强度和含水率的增大先增加后减小,随土壤粒径的增大而增大;在土壤含水率为40%、土壤粒径1~2 mm和电场强度12 V·cm⁻¹的条件下,加热6 h,HHCB去除效果最好,去除率达到了81.35%。通过响应曲面模拟优化得到的最佳工艺参数条件为,含水率39.07%、土壤粒径2.92 mm、电场强度12.64 V·cm⁻¹,在此条件下土壤HHCB的去除率为86.43%;在本实验条件下,3个因素对土壤HHCB去除率的影响为：含水率>土壤粒径>电场强度。本研究结果可为多环麝香污染土壤的修复提供参考。     

Control Technologies for Remediation of Contaminated Soil and Waste Deposits at Superf und Lead Battery Recycling Sites

This paper primarily addresses remediation of contaminated soils and waste deposits at defunct lead-acid battery recycling sites (LBRS) via immobilization and separation processes. A defunct LBRS is a facility at which battery breaking, secondary lead smelting, or both operations were performed for the primary purpose of reclaiming lead from spent lead-acid batteries. Metallic lead and lead compounds are generally the principal contaminants of concern in soils and waste deposits (i.e., buried, piled, landfilled waste) at these sites. Other metals (e.g., cadmium, copper, arsenic, antimony, and selenium) are often present at LBRS, but usually at much lower concentrations than lead and often present below hazardous concentrations. This article is primarily based on experience gained from: (1) Superfund site investigation, removal, and remedial actions, and (2) development and demonstration of control technologies under the Superfund Innovative Technology Evaluation (SITE) Program. The primary remedial options for lead contaminated soils and waste deposits include: (1) no action, (2) off-site disposal, (3) containment, (4) immobilization, (5) separation with resource recovery, and (6) separation without resource recovery. In spite of the toxicity of lead at low concentrations, the relative immobility of lead and site-specific risk assessments can still result in the selection of no action or containment remedies. Solidification/stabilization of lead-contaminated soils has been implemented at three Superfund sites and is the selected remedy at several others. Separation technologies (e.g., screening, extraction) are attractive because, if successful, they actually remove the contaminant from the environmental media. Separation technologies also offer the possibility that a valuable product (e.g., lead, plastic, energy) can be recovered, but careful consideration of economic and technical factors are required. Compared to the implementation of containment and solidification I stabilization remedies, separation technologies tend to be relatively novel, complex, and costly.     

Comparison of Microbial Pyrene and Benzo[a]Pyrene Mineralization in Liquid Medium,Soil Slurry,and Soil

The microbial degradation of ¹⁴C-pyrene and ¹⁴C-benzo[a]pyrene by a bacterial mixed culture was studied within a mixture of the PAHs phenanthrene, anthracene, pyrene, fluoranthene, and benzo[a]pyrene as sole carbon source in the different culture systems: (i) liquid medium, (ii) soil slurry (surface and grinding influence), and (iii) soil. The fate of these two labeled compounds was followed in these systems with an emphasis on mineralization to carbon dioxide, extractability, and adsorption to humic materials and formation of unextractable residual. Mineralization showed the most obvious differences: soil slurries achieved the best results both concerning the extent of mineralization and the time required. The highest extent of pyrene mineralization (54% within 21 days) was observed in soil slurries; in liquid media, pyrene mineralization was slower, but reached approximately the same extent (54% in 150 days); in soils, mineralization reached only 36% of added pyrene after 160 days. Benzo[a]pyrene was mineralized in a mixture of PAHs in soil slurries to an extent of 34% within 70 days, whereas mineralization in liquid medium and soil occurred in the range of 5% (70 days). Mineralization of benzo[a]pyrene in sand slurries was lower compared to soil slurries (19% in sand slurries vs. 32% in soil slurries within 50 days).     

Results of Treatment Evaluations of a Contaminated Synthetic Soil

Under Phase I of EPA’s Superfund soil treatability research program, which was conducted from April to November 1987, a surrogate soil containing a wide range of chemical contaminants typically occurring at Superfund sites was prepared and subjected to bench- or pilot-scale performance evaluations using the following treatment technologies: 1) physical separation/volume reduction (soil washing); 2) chemical treatment (KPEG); 3) thermal desorption; 4 ) incineration; and 5) stabilization/fixation. This report covers the formulation and development of the surrogate soil; it also highlights the results of the five treatment evaluations. Virtually all of the analytical data underlying this research were developed using EPA-SW846 methods. Detailed project reports covering the findings of each study are available through EPA’s Risk Reduction Engineering Laboratory in Cincinnati, Ohio.     

A Field Demonstration of the UV/Oxidation Technology to Treat Ground Water Contaminated with VOCs

This paper presents the Geld evaluation results of the ultraviolet radiation (UV)/oxidation technology developed by Ultrox International, Santa Ana, California. The Geld evaluation was performed at the Lorentz Barrel and Drum (LB&D) site in San Jose, California, under the Superfund Innovative Technology Evaluation program in February and March of 1989.

The UV/oxidation technology uses UV radiation, ozone, and hydrogen peroxide to oxidize organic contaminants present in water. At the LB&D site, this technology was evaluated in treating ground water contaminated with volatile organic compounds (VOCs). The Ultrox system achieved VOC removals greater than 90 percent. Most VOCs were removed through chemical oxidation. However, for a few VOCs, such as 1, 1, 1-trichloroethane and 1, 1-dichloroethane, stripping also contributed toward removal. The treated ground water met the applicable discharge standards for discharge into a local waterway at 95 percent confidence level. There were no harmful air emissions to the atmosphere from the Ultrox system, which is equipped with an off-gas treatment unit.     

SITE Demonstration of Slurry-Phase Biodegradation of PAH Contaminated Soil

This paper summarizes a joint Superfund Innovative Technology Evaluation (SITE) project on slurry-phase biodegradation and a project to collect information for the data base on Best Demonstrated Available Technologies (BOAT). In this 12-week study, a creosote contaminated soil from the Burlington Northern Superfund site in Brainerd, Minnesota was used to evaluate the effectiveness of the bioslurry reactors. During the demonstration, five 64-liter stainless steel bioreactors, equipped with agitation, aeration and temperature controls were used. The pilot scale study employed a 30 percent slurry, an inoculum of indigenous polynuclear aromatic hydrocarbon (PAH) degraders, and inorganic nutrients.

Total PAH degradation averaged 93.4 ± 3.2 percent over all five operating reactors in the 12 weeks with 97.4 percent degradation of the 2- and 3-ring PAHs and 90 percent degradation of the 4- to 6-ring PAHs. A study of the air emissions, both semivolatile compounds such as naphthalene, anthracene, and phenanthrene and volatile compounds such as toluene, xylene, and benzene, from the units showed that the greatest amount of emissions occurred during the loading of the reactors and during the first few days of operation. Therefore, it may not be cost-effective to require elaborate emissions controls unless there are significant quantities of volatile compounds present in the soil or water to be treated in a bioslurry reactor system.     

Variations of Bacterial Community Structure in Flooded Paddy Soil Contaminated with Herbicide Quinclorac

The denaturing gradient gel electrophoresis (DGGE) method was applied to determine the relative genetic complexity of microbial communities in flooded paddy soil treated with herbicide quinclorac (3,7-dichloro-8-quinoline-carboylic acid). The results obtained showed a significant effect of quinclorac on the development of bacterial populations in soils contaminated with different concentrations of the herbicide at the early time after application. In general, however, the number of populations of the same soil sample treated with the same concentration of the quinclorac differed obviously with increasing incubation time within the early 8 weeks. The scale of differences in banding patterns-showed that the microbial community structures of the quinclorac-treated and non-quinclorac-treated soils were not significantly different after 21 weeks of incubation. Quantification, as demonstrated in this paper, was studied by establishing dose-response relationships. Significant pattern variations were quantified. Prominent DGGE bands were excised, cloned and sequenced to gain insight into the identities of predominant bacterial populations. The majority of DGGE band sequences were related to bacterial genera Clostridium, Sphingobacterium, Xanthomonas and Rhodococcus.     

The Demonstration of Remedial Action Technologies for Contaminated Land and Ground water

The problem of contamination to land and groundwater from improper handling of hazardous materials/ waste is faced by all countries. Also, the need for reliable, cost-effective technologies to address this problem at contaminated sites exists throughout the world. Many countries have only started to develop new innovative/ alternative technologies while others have already started to apply these technologies to the cleanup of contaminated sites. The purpose of this NATO/ CCMS (North Atlantic Treaty Organization/Committee for the Challenges to Modern Society) Pilot Study is to discuss and evaluate new innovative/alternative technologies and/or existing systems that may be applicable to the cleanup of contaminated sites. Through this pilot study, the exchange of information on new and existing technologies for dealing with problem hazardous waste sites is promoted. The pilot study is made up of an international group of experts drawn from the participating countries. The study, which was initiated in 1986, is planned to last five years. It is piloted by the United States and copiloted by the Federal Republic of Germany (FRG) and The Netherlands.

This report includes an overview and history of the NATO/CCMS Pilot Study, but it primarily presents a documentation of the NATO/CCMS Second International Conference on the Demonstration of Remedial Action Technologies for Contaminated Land and Groundwater held in Bilthoven, The Netherlands on November 7-11,1988.     

Establishing and Evaluating the Risk Implications of Uniform Soil Remediation Goals

Abstract

There is growing interest in the establishment of uniform, concentration-based soil remediation goals to accelerate the cleanup of contaminated sites and to provide consistency in the extent of cleanup required for similar sites. If uniform goals are used in a region, post-remediation risk will vary across sites due to regional variability in site properties. Thus far, of the national and state agencies that have established or proposed uniform concentration guidelines, none have quantified the regional variability in risk that is likely to result with their use as remediation goals.

This paper describes a methodology for evaluating regional cancer risk variability resulting from use of uniform, concentration-based soil remediation goals, presents an example application of the methodology, and examines its utility for establishing uniform goals for organic contaminants in soil. The methodology is based on the integrated transport, fate, exposure, and risk model SoilRisk. Also addressed is the issue of contaminants for which regional risk variability is expected to be large with use of uniform soil remediation goals. An approach is described for reducing such variability by development of alternative uniform contaminant concentration levels for categories of sites differentiated by site geographic location or physical-chemical properties.     

Remediation of waters contaminated with pentachlorophenol

We describe a simple method of remediating waters contaminated with pentachlorophenol (PCP), which involves filtering the water through clean soil. The filtrate is contaminant free and no PCP can be extracted from the soil. If the soil it treated with dilute acid, the filtrate is still contaminant free but 28.7% of the PCP can be extracted from the contaminated soil. Irradiating the soil with microwave energy either destroys or binds the PCP to the soil irreversibly such that none can be extracted after long periods of time.     

Soil Gas Methane at Petroleum Contaminated Sites: Forensic Determination of Origin and Source

Hydrocarbon vapors associated with spilled petroleum products arouse regulatory concern and can pose a significant health and safety risk. While petroleum products do not contain a significant amount of methane (CH 4 ), high CH 4 contents in soil gas near petroleum spills have been reported. While CH 4 is nontoxic, its accumulation in shallow soil gas represents a potential explosion and asphyxiation hazard, especially in confined spaces. Identifying the source and origin of shallow CH 4 accumulations is an important part of evaluating potential exposure pathways, selecting appropriate remedial measures, and determining environmental liability. This paper discusses the potential nature and anthropogenic sources for shallow CH 4 and how integration of geological, geochemical, and land use data can be used to determine its origin and identify its source. Two case studies are presented, one where CH 4 associated with a gasoline spill is shown to be derived from a natural source rather than the gasoline, and a second where CH 4 associated with spilled crude oil is shown to be produced in the vadose zone by biodegradation of the oil.     

Soil Gas Methane at Petroleum Contaminated Sites: Forensic Determination of Origin and Source

Hydrocarbon vapors associated with spilled petroleum products arouse regulatory concern and can pose a significant health and safety risk. While petroleum products do not contain a significant amount of methane (CH₄), high CH₄contents in soil gas near petroleum spills have been reported. While CH₄is nontoxic, its accumulation in shallow soil gas represents a potential explosion and asphyxiation hazard, especially in confined spaces. Identifying the source and origin of shallow CH₄accumulations is an important part of evaluating potential exposure pathways, selecting appropriate remedial measures, and determining environmental liability. This paper discusses the potential nature and anthropogenic sources for shallow CH₄and how integration of geological, geochemical, and land use data can be used to determine its origin and identify its source. Two case studies are presented, one where CH₄associated with a gasoline spill is shown to be derived from a natural source rather than the gasoline, and a second where CH₄associated with spilled crude oil is shown to be produced in the vadose zone by biodegradation of the oil.     

Phytoavailability and Fractions of Iron and Manganese in Calcareous Soil Amended with Composted Urban Wastes

Little is known about the effects of applying composted urban wastes on the phytoavailability and distribution of iron (Fe) and manganese (Mn) among chemical fractions in soil. In order to study this concern several experiments in pots containing calcareous soil were carried out. The received treatments by adding separately two rates (20 and 80 Mg ha^?1) of municipal solid waste (MSW) compost and/or municipal solid waste and sewage sludge (MSW-SS) co-compost. The cropping sequence was a lettuce crop followed by a barley crop. It was observed that treatments amended with composted urban wastes tended to promote slight increases in lettuce yield compared to the control. The highest Fe levels in lettuce were found when higher rates of MSW-SS co-compost were applied; these values were significant compared to those obtained in the other treatments. In all cases, the application of organic materials increased the concentration and uptake of Mn in lettuce compared to the control; however, these increases were significant only when higher rates of MSW compost were applied. The organic amendments had beneficial delayed effects on barley yields, showing, in most cases, significant increases compared to the control. In this context, treatments with MSW compost were found to be more effective than the equivalent treatments amended with MSW-SS co-compost. Compared to the control, composted urban wastes increased Fe concentration in straw and rachis, and decreased Fe concentration in barley grain. Similarly, a decreased concentration of Mn in the dry matter of barley crop grown in soils treated with composted urban wastes was observed.     

Remediation of metal contaminated soil with mineral-amended composts

This study examined the use of two composts derived from green waste and sewage sludge, amended with minerals (clinoptilolite or bentonite), for the remediation of metal-contaminated brownfield sites to transform them into greenspace. Soils contaminated with high or low levels of metals were mixed with the mineral-enhanced composts at different ratios and assessed by leaching tests, biomass production and metal accumulation of ryegrass (Lolium perenne L.). The results showed that the green waste compost reduced the leaching of Cd and Zn up to 48% whereas the composted sewage sludge doubled the leachate concentration of Zn. However, the same soil amended with composted sewage sludge showed an efficient reduction in plant concentrations of Cd, Cu, Pb or Zn by up to 80%. The results suggest that metal immobilisation and bioavailability are governed by the formation of complexes between the metals and organic matter. The amendment with minerals had only limited effects.