淋洗修复重金属和多环芳烃复合污染土壤的研究进展

重金属和多环芳烃（PAHs）常共存于土壤中形成复合污染。作为典型无机污染物和有机污染物的代表,淋洗法可同时有效去除这两类污染物,具有良好的发展前景。本文结合国内外的研究成果,从重金属和PAHs在环境中的行为着手,重点论述了常用淋洗剂的种类、去除机理和优缺点,分析了影响复合污染物去除效果的主要因素,并对今后该技术的发展方向进行了展望。     

Functions of Straw for In Situ Remediation of Acidic Mining Lakes

The addition of straw in combination with Carbokalk, a by-product from the sugar-industry, was successfully used to stimulate microbial alkalinity generation in an acidic mining lake. To get detailed information about functions of straw, anenclosure experiment was carried out. Straw bundles were placedat the sediment surface of an acidic mining lake (ML 111) and thephysiochemical conditions and the microbiology of the sediment-water contact zone were studied. Straw was degraded by anaerobic microorganisms and dissolved organic carbon (DOC) leached from straw bundles. Pigmented flagellates responded to the DOC supply in the water column anda considerable amount of algal carbon was transported to the sediment. Straw addition led to microbial reduction of iron andsulfate in the sediment. Sulfate reduction was observed at a pHof 5.5. The pH, however, was not high enough to precipitate H₂S completely. Thus, some H₂S diffused into the watercolumn, where it was reoxidized. Straw did not create orstabilize an anoxic water body above the sediment. Microbial sulfate reduction and pyrite formation only took place in the sediment,whereas iron reduction also took place in the straw. Straw, however, altered the flow conditions above the sediment surfaceand prevented complete mixing of the profundal water. Straw didnot serve as a substratum for a reactive biofilm. We conclude that the most important function of straw for mining lake remediation is to be a long-term nutrient source for microbialalkalinity generation in the sediment.     

In situ remediation of MTBE utilizing ozone

There has been a great deal of focus on methyl tertiary butyl ether (MTBE) over the past few years by local, state, and federal government, industry, public stakeholders, the environmental services market, and educational institutions. This focus is, in large part, the result of the widespread detection of MTBE in groundwater and surface waters across the United States. The presence of MTBE in groundwater has been attributed primarily to the release from underground storage tank (UST) systems at gasoline service stations. MTBE's physical and chemical properties are different than other constituents of gasoline that have traditionally been cause for concern [benzene, toluene, ethylbenzene, and xylenes (BTEX)]. This difference in properties is why MTBE migrates differently in the subsurface environment and exhibits different constraints relative to mitigation and remediation of MTBE once it has been released to subsurface soils and groundwater. Resource Control Corporation (RCC) has accomplished the remediation of MTBE from subsurface soil and groundwater at multiple sites using ozone. RCC has successfully applied ozone at several sites with different lithologies, geochemistry, and concentrations of constituents of concern. This article presents results from several projects utilizing in situ chemical oxidation with ozone. On these projects MTBE concentrations in groundwater were reduced to remedial objectives usually sooner than anticipated. © 2002 Wiley Periodicals, Inc.     

Microbially Mediated In Situ Desorption Accelerates Remediation of Large Gasoline Product Plume

Remediation of a large separate‐phase hydrocarbon product and associated dissolved‐phase gasoline plume was accelerated by coupling multiphase extraction with in situ microbial stimulation. At the beginning of remediation activities, the separate‐phase hydrocarbon plume extended an estimated seven acres with product thickness measuring up to 2.1 feet thick. Within 18 months after beginning extraction, reduction of gasoline constituents in groundwater became asymptotic and measureable product disappeared from the upgradient source area. At that time, the remediation team initiated a program of limited in situ anaerobic bioremediation with the goal of stimulating production of natural surfactants from native microbes to release petroleum from the soil matrix. Groundwater concentrations of gasoline constituents increased gradually over the next three years, improving recovery without biofouling the pump‐and‐treat infrastructure. Using this approach, the groundwater component of the remedy was completed in less than five years, substantially less than the 10 years to 15 years predicted by modeling. This strategy demonstrated a more sustainable approach to remediation, reducing electrical usage by an estimated 800 megawatt hours, reducing infrastructure requirements, and preserving an estimated 150 million gallons of groundwater for this arid agricultural area. © 2014 Wiley Periodicals, Inc.     

In situ remediation of arsenic in contaminated soils

In situ chemical fixation represents a promising and potentially cost‐effective treatment alternative for metal‐contaminated soils. This article presents the findings of the use of iron‐bearing soil amendments to reduce the leachability and bioaccessibility of arsenic in soils impacted by stack fallout from a zinc smelter. The focus of this investigation was to reduce the lead bioaccessibility of the soils through addition with phosphorus‐bearing amendments. However, as phosphorus addition was expected to increase arsenic mobility, the fixation strategy also incorporated use of iron‐bearing amendments to offset or reverse these effects. The findings of this investigation demonstrated that inclusion of iron‐bearing chemicals in the amendment formulation reduced arsenic leachability and bioaccessibility without compromising amendment effectiveness for reducing lead bioaccessibility. These results suggest that in situ chemical fixation has the potential to be an effective strategy for treatment of the impacted soils. © 2003 Wiley Periodicals, Inc.     

In Situ Remediation of 1,4‐Dioxane Using Electrical Resistance Heating

Recent regulatory changes need more challenging treatment goals for 1,4‐dioxane. However, significant treatment limitations exist in part due to the high solubility and low Henry's law constant of 1,4‐dioxane. Two case studies are reported with substantial 1,4‐dioxane concentration reductions through in situ thermal remediation via electrical resistance heating (ERH). Concentration reductions greater than 99.8 percent of 1,4‐dioxane have been observed in the field using ERH. Concentrations of 1,4‐dioxane in air and steam extracted by an ERH vapor recovery system have also been evaluated. Laboratory studies were conducted to further understand the mechanisms that enable ERH remediation of 1,4‐dioxane. Vapor liquid equilibrium studies in water and soil were conducted and utilized to develop an ERH treatment cost model for 1,4‐dioxane. Existing field data were correlated to the 1,4‐dioxane treatment cost model. Field observations and laboratory testing indicate steam stripping that occurs through ERH remediation is an effective treatment method for 1,4‐dioxane. ©2015 Wiley Periodicals, Inc.     

In situ ammonia removal in bioreactor landfill leachate

Although bioreactor landfills have many advantages associated with them, challenges remain, including the persistence of NH(3)-N in the leachate. Because NH(3)-N is both persistent and toxic, it will likely influence when the landfill is biologically stable and when post-closure monitoring may end. An in situ nitrogen removal technique would be advantageous. Recent studies have shown the efficacy of such processes; however, they are lacking the data required to enable adequate implementation at field-scale bioreactor landfills. Research was conducted to evaluate the kinetics of in situ ammonia removal in both acclimated and unacclimated wastes to aid in developing guidance for field-scale implementation. Results demonstrate that in situ nitrification is feasible in an aerated solid waste environment and that the potential for simultaneous nitrification and denitrification (even under low biodegradable C:N conditions) in field-scale bioreactor landfills is significant due to the presence of both aerobic and anoxic areas. All rate data fit well to Monod kinetics, with specific rates of removal of 0.196 and 0.117 mgN/day-g dry waste and half-saturation constants of 59.6 and 147 mgN/L for acclimated and unacclimated wastes, respectively. Although specific rates of ammonia removal in the unacclimated waste are lower than in the acclimated waste, a relatively quick start-up of ammonia removal was observed in the unacclimated waste. Using the removal rate expressions developed will allow for estimation of the treatment times and volumes necessary to remove NH(3)-N from recirculated landfill leachate.     

In situ burning of emulsions R&D in Norway

SINTEF Applied Chemistry has been working in the field of in situ burning since 1988, beginning with the first open water testing of the 3M fire proof boom which took place on Spitsbergen. In recent years, the focus of SINTEF's research activities in this area has been on the burning of emulsions. An experimental programme was initiated by NOFO in 1990 to study the in situ burning of water-in-oil (w/o) emulsions, as part of a wider NOFO programme ‘Oil spill contingency in Northern and Arctic waters’ (ONA). The research conducted under this programme has addressed many areas of in situ burning including:

• •• study of processes governing burning emulsions
• •• development of ignition techniques for emulsions
• •• effect of environmental conditions on burning
• •• burning crude oil and emulsions in broken ice
• •• uncontained burning of crude oil and emulsions.

     

In situ hypochlorous acid generation for the treatment of syntan wastewater

A new treatment process was employed to treat wastewater generated from a factory manufacturing syntan (synthetic tannin). In this treatment process, in-situ production of hypochlorous acid was achieved by the use of an aqueous sodium chloride solution for chlorine production. As the graphite anode and stainless steel cathode zones were kept unseparated, the hypochlorous acid was produced by electrolysis. The hypochlorous acid was utilized for the oxidation of organic matter present in the wastewater. The results showed that for an initial COD concentration of 10,000 mg/l, a turbidity of 277 NTU, a tannin concentration of 4000 mg/l, a temperature of 27±1°C, a current density of 42.5 mA/cm², a sodium chloride content of 3% and an electrolysis period of 210 min showed an effluent COD concentration of 230 mg/l, a turbidity of 9 NTU, a tannin concentration below the detection limit and a temperature of 37±2°C.     

In situ chemical oxidation: Lessons learned at multiple sites

This paper compiles a detailed set of in situ chemical oxidation (ISCO) lessons learned pertaining to design, execution, and safety based on global experiences over the last 20 years. While the benefits of a “correct” application are known (e.g., cost effectiveness, speed, permanence of treatment), history also provides examples of a variety of “incorrect” applications. These provide an opportunity to highlight recurring themes that resulted in failures. ISCO is, and will continue to provide, an important remedial tool for site remediation, particularly as a component of a multifaceted approach for addressing large and complex sites. Future success, however, requires an objective understanding of both the benefits and the limitations of the technology. The ability to learn from the mistakes of the past provides an opportunity to eliminate, or at least minimize, them in the future. Over the last 25 years of ISCO application, process understanding and knowledge have improved and evolved. This paper combines a thorough discussion of lessons learned through decades of ISCO implementation throughout all aspects of ISCO projects with an analysis of changes to the ISCO remediation market. By discussing the interplay of these two themes and providing recommendations from collective lessons learned, we hope to improve the future of safe, cost‐effective, and successful applications of ISCO.     

In situ bioremediation of an aniline spill in an industrial setting

In situ remediation of aniline from soils and groundwater using biological and physical treatments was conducted at the BASF Corporation facility in Geismar, Louisiana. To mitigate the migration of aniline, remediate contaminated soil and groundwater, and determine concentrations, 24 immobilized microbe bioreactors were fixed in the subsoil, and a horizontal recovery well and 7 monitoring wells were installed. Soil and monitoring wells were sampled quarterly to assess bioplug impact on the aniline concentrations. The recovery well was sampled monthly to estimate the pounds of aniline removed from groundwater. Soil pH, composition, and microbial counts were used to estimate the fate and transport. Aniline levels were lowered significantly after remediation and total cancer risk was below levels for industrial sites, as established by State of Louisiana Risk Evaluation/Corrective Action Program guidelines. © 2010 Wiley Periodicals, Inc.     

In situ thermal remediation of DNAPL and LNAPL using electrical resistance heating

Electrical resistance heating (ERH) is an in situ treatment for soil and groundwater remediation that can reduce the time to clean up volatile organic compounds (VOCs) from years to months. The technology is now mature enough to provide site owners with both performance and financial certainty in their site‐closure process. The ability of the technology to remediate soil and groundwater impacted by chlorinated solvents and petroleum hydrocarbons regardless of lithology proves to be beneficial over conventional in situ technologies that are dependent on advective flow. These conventional technologies include: soil vapor recovery, air sparging, and pumpand‐treat, or the delivery of fluids to the subsurface such as chemical oxidization and bioremediation. The technology is very tolerant of subsurface heterogeneities and actually performs as well in low‐permeability silts and clay as in higher‐ permeability sands and gravels. ERH is often implemented around and under buildings and public access areas without upsetting normal business operations. ERH may also be combined with other treatment technologies to optimize and enhance their performance. This article describes how the technology was developed, how it works, and provides two case studies where ERH was used to remediate complex lithologies. © 2005 Wiley Periodicals, Inc.     

In situ nitrogen removal from leachate by bioreactor landfill with limited aeration

The feasibility of simultaneous nitrification and denitrification in a bioreactor landfill with limited aeration was assessed. Three column reactors, simulating bioreactor landfill operations under anaerobic condition (as reference), intermittent forced aeration and enhanced natural aeration were hence established, where aerated columns passed through two phases, i.e., fresh landfill and well-decomposed landfill. The experimental results show that limited aeration decreased nitrogen loadings of leachate distinctly in the fresh landfill. In the well-decomposed landfill, the NH(4)(+)-N of the input leachate could be nitrified completely in the aerated landfill columns. The nitrifying loadings of the column cross section reached 7.9 g N/m(2)d and 16.9 g N/m(2)d in the simulated landfill columns of intermittent forced aeration and enhanced natural aeration, respectively. The denitrification was influenced by oxygen distribution in the landfill column. Intermittent existence of oxygen in the landfill with the intermittent forced aeration was favorable to denitrify the NO(2)(-)-N and NO(3)(-)-N, indicated by the high denitrification efficiency (>99%) under the condition of BOD(5)/TN of more than 5.4 in leachate; locally persistent existence of oxygen in the landfill with enhanced natural aeration could limit the denitrification, indicated by relatively low denitrification efficiency of about 75% even when the BOD(5)/TN in leachate had an average of 7.1.     

Remediation of sites contaminated with TCE

Widespread use of trichloroethylene (TCE) in the U.S. has resulted in its frequent detection in soil and groundwater. TCE can become a health hazard after being processed in the human liver; or reductive dehalogenation in the environment may result in production of vinyl chloride, a known carcinogen. This has generated a high degree of interest in efficient and cost-effective technologies that can be used to remediate soil and ground-water contaminated with TCE. The purpose of this paper is to present and discuss relevant physicochemical properties and reactive mechanisms of TCE, and to delineate and discuss promising remediation methodologies that have been proposed and/or demonstrated for restoring contaminated subsurface environments. The information in this article has been funded wholly or in part by the U.S. EPA under contract No. 68–C8–0058 to Dynamac Corporation; it has been subjected to the Agency's peer and administrative review process and approved for publication.     

Remediation of metal-contaminated sites using plants

Heavy metal contamination of soil resulting from anthropogenic sources poses a significant challenge in many industrialized societies. The current technologies employed for removal of heavy metals often involve expensive ex-situ processes requiring sophisticated equipment and removal, transportation, and purification of the soil. Generally, in-situ remedial technologies are favored to ex-situ methods for detoxification, neutralization, degradation, or immobilization of contaminants. In-situ bioremediation is increasingly favored because of its effectiveness and low cost. A new type of bioremediation, known as vegetative remediation or “phytoremediation,” uses metal-tolerant hyperaccumulator plants to take up metal ions from soils and store them in their aboveground parts. To select the appropriate phytoremediation technology, one must understand the technical feasibility, cost effectiveness, and availability of the suitable plant species. Equally important is determining whether the site's soil conditions are optimal to enhance or restore the soil biological activity. Before phytoremediation can be exploited on a contaminated site, greenhouse-scale confirmatory testing is necessary to measure plant uptake and correlate shoot metal concentrations to available soil metals. These tests also validate that the harvesting and subsequent disposal of metal-containing plant tissues are environmentally safe and manageable.     

In situ soil stabilization for source control of a lithium and bromate groundwater plume

Historic mineral ore processing operations at the former Cyprus Foote Mineral Site located in East Whiteland Township, Pennsylvania, have resulted in the creation of an approximately 10,000‐foot‐long off‐site groundwater plume impacted with lithium and bromate. The plume emanating from the site is impacting the groundwater quality of downgradient private residences. As an early part of the remedial implementation, the private residences were provided with public water connections while the source control efforts were being designed and implemented. Bromate and lithium have recently emerged as groundwater contaminants subjected to increased regulatory scrutiny. This is evidenced in a recently lowered Federal Maximum Contaminant Level (MCL) for bromate of 0.010 milligrams per liter and a Medium‐Specific Concentration (MSC) of 0.005 mg/L for lithium recently proposed by the Pennsylvania Department of Environmental Protection (PADEP) for all groundwater within the Commonwealth. Elevated concentrations for bromate and lithium were detected above the Proposed Remediation Goals (PRGs) for the site, MCLs, and MSCs at a distance of 7,300 feet and 9,200 feet from the source area, respectively. To reduce the contaminant concentrations within the groundwater plume, which will ultimately result in a regressing plume, and to enable the Brownfield redevelopment of this Superfund site, auger‐based, in situ soil stabilization (ISS) with depths of up to 75 feet below ground surface (bgs) was selected as the remedy. The remedial implementation required the temporary removal and relocation of over 100,000 cubic yards of overburden to expose the lithium‐bearing tailings prior to treatment. Using customized 90‐foot‐long, 9‐foot‐diameter augers attached to cranes and drilling platforms, ancillary support excavators, and approximately 21,000 tons of reagent; 2,019 ISS columns were advanced to depths ranging from 10 to 74 feet bgs. This resulted in the creation of an in situ low‐permeablity 117,045‐yd³ “quasi‐monolith,” which encompasses a lateral extent of approximately three acres. The integration of a comprehensive ISS design with a comprehensive long‐term groundwater‐monitoring plan ensured the success of the ISS implementation and will enable a continued evaluation of the off‐site groundwater quality. © 2009 Wiley Periodicals, Inc.     

In situ treatment of a dilute chlorinated solvent plume in an acidic aerobic aquifer

In situ bioremediation was selected in the Record of Decision (ROD) as the remedial technology for a 29‐acre dilute, acidic and aerobic, chlorinated solvent plume (principally trichloroethylene [TCE] and 1,1‐dichloroethylene) for a Superfund site located in central New Jersey. Implementation of the remedy at full‐scale began in late 2010, using reductive dechlorination and bioaugmentation, and treatment has continued steadily over the last 9 years. The amendments injected include electron donor and alkaline (bicarbonate) buffer solution and, once anaerobic aquifer conditions became established, a bioaugmentation culture. Amendment injections occurred in multilevel injection wells (IWs), to maintain control over the vertical interval of amendment delivery. The areal coverage of the plume has been reduced by 59% based on the 10 µg/L TCE isocontour and the contaminant mass has been reduced by 79% through the 9 years of treatment. Lessons learned from this project include the need for bioaugmentation in the acidic aquifer and an efficient and effective manner of well construction and amendment injection using multiscreen single casing IWs and packer systems. Additional lessons learned include differences in longevity of the electron donor amendment versus the bicarbonate neutralization additive, and the need for varied amendment delivery techniques (IWs, direct injection, horizontal well installation) in selected lower permeable zones to attain treatment.     

Remediation of MTBE-Contaminated Water and Soil

As the number of leaking underground fuel tank sites with methyl tertiary butyl ehter (MTBE) contamination continues to grow, there is a need to develop cost-effective solutions for treatment of soil and water contamination. MTBE poses special challenges because of its physicochemical properties, in particular high solubility and low Henry's constant, low affinity for sorption, and very slow rate of microbial degradation. Advanced oxidation processes tend to generate undesirable by-products. Based on laboratory studies with hollow fiber membranes (HFM), a field-scale unit was constructed and tested at a number of sites, to determine the effectiveness of this technology in dealing with MTBE contamination. In addition, to treat the soil contamination, the HFM unit was coupled with a Spray Aeration Vapor Extraction (SAVE) unit, which is based on an internal combustion engine. The engine provides the means to treat soil vapors, as well as organic vapors from the spray aeration and HFM units. The overall treatment objectives of 5μg/l for MTBE and 1 μg/l for benzene were achieved with a treatment train consisting of an ion exchange unit, a spray aeration system, a hollow fiber membrane module and two granular activated carbon (GAC) units, for flowrates ranging from 3.8 to 30 l/min (1 to 8 gal/min). The ion exchange unit sewed to reduce water hardness and avoid scaling in the subsequent treatment units, extending the run-time of the entire system. Overall removal efficiencies for the spray aeration system and hollow fiber membrane module ranged from 85 to over 99 percent. High removal efficiencies (> 97%) were obtained at elevated water temperatures (54°C) or lower flowrates (up to 11 l/min). The GAC units were used only to polish the effluent and meet the discharge requirements. Soil, water, and gas phases are treated with this system. Cost estimates are provided for similar treatment processes, for water flowrates up to 38 l/min (10 gal/min). © 1999 John Wiley & Sons, Inc.