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Innovations in Ground Water and Soil Cleanup: From Concept to Commercialization 3 State of the Practice of Ground Water and Soil Remediation Innovation in the environmental industry is driven by the need to solve difficult problems and the desire to improve upon existing solutions. When a ground water or soil cleanup technology is developed and applied, frequently in response to an unsolved problem, its acceptance and application are often limited initially to specific contaminants and specific hydrogeologic conditions. As the technology matures, it typically addresses the same range of contaminant types, but its range of application in subsurface environments becomes better defined. This evolutionary process is similar for most remediation technologies, but the rate at which new technologies are adopted varies considerably. For example, soil vapor extraction (SVE) technologies, used for removing volatile contaminants from soil, were virtually unused at Superfund sites in 1985 but by 1995 had been selected for source control at 20 percent of Superfund sites (EPA, 1996a). However, for other technologies, especially those for cleaning up contaminants in situ, this evolution is occurring much more slowly than one would predict based on the large number of contaminated sites and the hundreds of billions of dollars in projected cleanup costs for these sites. There is no shortage of new ideas for improving the ability to restore contaminated ground water and soil. However, for reasons explained in Chapter 2, successful commercialization of all but a few new ideas has been limited. This chapter reviews the state of development of technologies for cleaning up ground water and soil, highlighting knowledge and information gaps, and describes challenges and strategies for cleaning up different types of contaminants. The chapter defines all technologies for cleaning up contaminants below the water table as "ground water cleanup technologies" and all technologies for cleaning up contaminants above the water table as "soil cleanup technologies." This dis-
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Innovations in Ground Water and Soil Cleanup: From Concept to Commercialization tinction is somewhat artificial, because many technologies for restoring areas below the water table address contaminated geologic materials rather than the water itself. Nevertheless, although these technologies do not specifically treat the water, but rather contaminants in the geologic materials, users of the technologies generally refer to them as ground water cleanup technologies because their primary intent is to prevent the contaminants from dissolving in and contaminating the ground water. Included in this chapter are technologies that treat ground water contaminants in place in the subsurface and soil technologies that treat the soil either in place or on site in a treatment unit. The chapter does not cover technologies for removing contaminants from ground water once it has been pumped to the surface. The challenge of removing contaminants from water at the surface has already been largely addressed through the development of systems for treating municipal and industrial wastewater. In comparison, relatively few technologies are available for removing contaminants from soil or geologic materials to which the contaminants have tightly bound. Even fewer technologies exist for treating contaminated ground water in place in the subsurface. Furthermore, the processes that can be exploited in these technologies are still not fully understood. WHAT IS INNOVATIVE REMEDIATION TECHNOLOGY? "Innovative technology" as applied to the cleanup of ground water and soil is an elusive term, for two primary reasons. First, government agency representatives and others involved in waste-site cleanup may have different perspectives on which technologies are innovative. For example, the Environmental Protection Agency's (EPA's) 1996 Innovative Treatment Technologies: Annual Status Report classifies in situ bioremediation of contaminated soils as an innovative technology, while the Air Force specifies bioventing (a type of in situ bioremediation) as the standard remedy for soils contaminated with petroleum hydrocarbons and other volatile organic compounds (DOD Environmental Technology Transfer Committee, 1994). The Department of Energy (DOE) considers any technology innovative if it has not been used at DOE sites (J. Walker, DOE, personal communication, 1995). Thus, the definition of innovative varies depending on the perspective of the user. A second reason why "innovative" is hard to define is that technologies are continually evolving. In the ground water and soil remediation business, only a few technologies represent true breakthroughs, in the sense that they apply concepts never before used in the field. More commonly, innovation occurs incrementally, evolving from existing technologies. This evolution is a product of several factors. The first factor is increased experience. As a technology is implemented at various sites, the experience gained provides a basis for defining and overcoming limitations, establishing best practices, and expanding the technology's application to new contamination problems. The second factor is com-
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Innovations in Ground Water and Soil Cleanup: From Concept to Commercialization petition, both among the technologies and among practitioners who design the technologies. The third factor is the technology's performance limitations. All technologies have practical limitations that affect their market viability; a given technology may not perform well initially for certain contaminant types and hydrogeologic settings, but as these limitations are addressed, the applicability and marketability of the technology may increase. The fourth factor is cross-fertilization with other technologies. A technique or even a whole new technology may be incorporated into an existing technology to improve its performance or overcome a limitation. The net result of this evolution is that remediation technologies go through a cyclical or generational life cycle. The first stage is the initial, and often crude, application of the technology. During this period, acceptance of the technology increases as it is successfully applied and its success is communicated. During the second stage of evolution, design practices for the technology become established. Acceptance and application grow rapidly as the benefit of the technology becomes known. The third stage is the mature, common practice of the technology. In this stage, the focus shifts from the benefits of the technology to its limitations, and acceptance and application may decline. During this mature application stage, the technology is vulnerable to replacement. However, use of the technology may increase again, either as its limitations are overcome or as the technology becomes applicable to new contaminant types and/or hydrogeologic settings. When a significant limitation is overcome, the technology enjoys a rebirth. The two best examples of remediation technologies that have developed through this evolutionary process are in situ bioremediation and SVE (see Boxes 3-1 and 3-2). This chapter reviews a broad range of remediation technologies other than those based on conventional pumping and treating of ground water or digging and either hauling or burning of soil. Many of the technologies discussed in the chapter, including SVE and in situ bioremediation, have a significant experience base and are not new. In addition, many are enhancements to conventional approaches rather than new developments. Nevertheless, all of these technologies have in common the ability (whether potential or proven) to increase the effectiveness and/or decrease the costs of subsurface cleanup when compared to the historical approaches of pumping and treating ground water and hauling or burning soil. AVAILABILITY OF INFORMATION ON INNOVATIVE REMEDIATION TECHNOLOGIES Application of innovative remediation technologies has been slowed by lack of uniform, synthesized information about remediation technology performance. While considerable effort is being invested in researching and developing remediation technologies, these efforts are often isolated and do not benefit the general industry because circulation of information is limited. Broad acceptance of a tech-
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Innovations in Ground Water and Soil Cleanup: From Concept to Commercialization BOX 3-1 Innovations in Engineered in Situ Bioremediation Engineered in situ bioremediation, the purposeful stimulation of microorganisms in ground water and soil to degrade contaminants, was first applied in 1972 to clean up a spill of gasoline from a pipeline in Ambler, Pennsylvania (Raymond et al., 1977). At that time, in situ bioremediation addressed the unsolved problem of residual petroleum contamination in soil and ground water. The related generations of technology that followed this first in situ bioremediation system focused primarily on petroleum hydrocarbons and were essentially water-based systems: both the oxygen and nutrients necessary to stimulate growth of contaminant-consuming organisms were supplied by circulating ground water. From 1972 to 1983, only about a dozen in situ bioremediation projects were conducted nationwide (Brown et al., 1993). Performance was limited by the low solubility of oxygen in water. The second generation of in situ bioremediation systems used hydrogen peroxide (H2 O2) to provide a more efficient method of supplying oxygen in soluble form. H2 O2 supplied 10 to 50 times more oxygen equivalents than did the existing aeration systems. The third-generation in situ bioremediation system employed SVE (see Box 3-2) to supply oxygen above the water table and used H2 O2 to provide oxygen below the water table. Both the second- and third-generation technologies were limited by the expense and difficulty of using H2 O2 , and there was a significant effort to find an alternative. Several alternatives to H2 O2 were explored, but the most successful was air sparging, which involves injecting air directly into the subsurface. Air sparging was initially developed as a separate technology to remove volatile contaminants by evaporative processes, but it was soon incorporated into bioremediation technology, sometimes called biosparging. Due in part to the success in improving oxygen delivery systems, in situ bioremediation systems are now in use at thousands of underground storage tank sites and dozens of Superfund sites (see Chapter 1). Parallel to the development of the different generations of in situ bioremediation systems for treatment of petroleum hydrocarbons has been the development of a number of spin-off technologies. The first of these was improved ex situ soil bioremediation technology. Ex situ bioremediation employs the principles and techniques of in situ bioremediation to treat excavated soils. A second improvement has been the increased understanding of bioremediation of chlorinated hydrocarbons, which was largely unknown until the mid-1980s (McCarty and Semprini, 1994). A third spin-off has been the development of intrinsic bioremediation (bioremediation without using engineered systems to stimulate native soil microbes) to control and mitigate contaminant plumes.
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Innovations in Ground Water and Soil Cleanup: From Concept to Commercialization Petroleum-contaminated soils being treated in above-ground bioremediation cells engineered with vapor extraction systems. Courtesy of Fluor Daniel GTI. nology requires documentation of the technology's performance and accessibility of performance information. Often in the development of remediation technology, data collection is minimal. As a result, much of the available information is anecdotal and empirical. This relative lack of documented performance data makes it difficult to judge the benefits and limitations of a technology without trying it. As a result, remediation technology development is somewhat repetitive, as individual practitioners tend to repeat the same work until the experience base is sufficiently distributed that knowledge of the technology is also well distributed. The lack of consistent information is pervasive in the remediation market and encompasses all of the following problems: technology reports are often incomplete; critical scientific evaluation of technology application most often is not conducted or is not conducted with the goal of collecting comparable data sets; reliable cost data are lacking and inconsistent; methods for determining costs and evaluating successes can vary enormously; and much information is proprietary. These factors combine to make it very difficult to conduct rigorous comparisons
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Innovations in Ground Water and Soil Cleanup: From Concept to Commercialization between technologies and across problem contexts with existing data. In addition, there are no complete, centralized data bases that cross markets and government programs. The 1995 publication Accessing Federal Data Bases for Contaminated Site CleanUp Technologies lists 25 different data bases that could be potentially useful in evaluating remediation technologies (Federal Remediation Technologies Roundtable, 1995a), but these data bases are not coordinated, and many of them are difficult to access (see Appendix A for a listing of data bases). In fact, the existence of such a large number of data bases in itself creates confusion, because the data bases contain information in different formats that may not be comparable, and the quality of the data from different data bases is variable and difficult to assess. A few programs exist or are developing to facilitate evaluation of technologies. The EPA's Technology Innovation Office is collecting information on Superfund technology selections. The Federal Remediation Technologies Roundtable (a consortium of federal agency personnel involved in remediation) has developed protocols for standardized cost evaluations (Federal Remediation Technologies Roundtable, 1995b). Joint programs between states allowing sharing of information collected for technology evaluation are being created, and the results from these programs should help alleviate some of the information deficit. The EPA has established the Ground Water Remediation Technologies Analysis Center to help disseminate information on new remediation technologies (GWRTAC, 1995). These efforts are useful for developing a global view of what categories of remediation technologies are being tested and implemented. However, the fact remains that there are few reports that contain well considered evaluations of technologies, rather than mere compilations of information lacking careful analysis. A few examples of thoughtful technology evaluation may serve as models for future work. The American Academy of Environmental Engineers' WASTECH® project has produced eight monographs of innovative waste-site remediation technologies. Generally, the scope of the analysis for this project was limited to technologies that are not commonly applied; have been sufficiently developed so that they can be used in full-scale applications; have sufficient data available to describe and explain the technology; and have sufficient data to assess effectiveness, limitations, and potential applications. An important contribution of this effort was applying such criteria to a wealth of information and synthesizing the findings by a task group of experts, whose work was peer reviewed, to produce a discussion of potential applications, process evaluations, limitations, and technology prognoses. Although restricted in scope and not uniform in coverage, the WASTECH® monographs provide a measure of consensus on performance of the technologies reviewed in the series; the philosophy and approach are laudable. A follow-up WASTECH® series of seven monographs emphasizing remediation technology design and implementation is in preparation. An example of a focused report on a particular problem context is Dávila et
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Innovations in Ground Water and Soil Cleanup: From Concept to Commercialization BOX 3-2 Innovations in Soil Vapor Extraction (SVE) SVE has been used to treat volatile hydrocarbons since the mid-1970s. Originally, the technology was used to remove vapors from soils to prevent the vapors from entering buildings. This first-generation technology was derived from methane collection systems employed at landfills and typically consisted of lateral collection pipes placed along building foundations. A vacuum was applied to these lateral pipes to collect the organic vapors. Engineers soon observed, however, that the removal of vapors led to significant contaminant mass removal and a reduction of the level of contamination in the soil. The second-generation (circa 1983) SVE technology focused specifically on the removal of volatile organic compounds (VOCs) from soil instead of the simpler collection of vapors. Two theories developed concerning SVE. The first postulated that the function of the vacuum was to ''vacuum distill" the VOCs from the soil matrix and was based on the principle that the boiling point of most VOCs decreases with decreasing pressure. With this approach, typically a high vacuum (greater than 500 mm, or 20 in., Hg) was applied to decrease the boiling point of the VOCs and allow them to volatilize. The second theory of SVE postulated that the process was an evaporative one. The purpose of the vacuum was to induce air flow through the subsurface to evaporate the VOCs. This theory has become the dominant SVE theory and is the basis for most SVE designs. The evaporative model uses low to moderate vacuums of less than 380 mm (15 in.) Hg. The main evolution of SVE has been in the design tools. The second-generation systems were typically designed on the basis of vacuum radius. Designers assumed that as long as there was a detectable vacuum, al. (1993), which discusses technology applications for cleanup of soil and sediment contaminated with polychlorinated biphenyls (PCBs). This report discusses succinctly a number of technologies from an engineering perspective, pointing to specific examples of successes and problems from field evaluations. A report by Grubb and Sitar (1994) that discusses in situ remediation of dense nonaqueousphase liquid (DNAPL) contaminants provides another example of a report that critically evaluates technologies for solving a particular type of contamination problem. A report by Troxler et al. (1992) on thermal desorption for petroleum-contaminated soils provides a useful perspective on a particular technology application and its status of development. Reports by Vidic and Pohland (1996) on in situ treatment walls and by Jafvert (1996) on cosolvent and surfactant flushing systems provide peer-reviewed evaluations of these technologies.
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Innovations in Ground Water and Soil Cleanup: From Concept to Commercialization there was sufficient air flow. With this simple design basis, however, many SVE systems proved less effective than planned. Designs based on simple vacuum readings do not reflect true air flow unless they are adjusted for air permeability using Darcy's law. Once models were used to adjust vacuum readings to actual air flow rates, the performance of SVE systems improved. In retrospect, use of air flow-based designs seems like an obvious improvement. However, implementation has not been easy because of the need to use flow models. While SVE has not evolved as extensively as bioremediation, it has engendered a much more varied set of spin-off technologies. This may be in part due to the clarity of the limitations of SVE, which removes volatile compounds from unsaturated soils by induced air flow. By this definition, there are three basic limitations: (1) the volatility of the contaminant, (2) the lack of air in saturated environments, and (3) the permeability of the soil matrix to air flow. The limitation of volatility has fostered two other innovations. The first is the use of thermal energy to increase the contaminant volatility. Thermal systems under development use hot air, steam, radio waves, microwaves, or electrical resistance to heat the soil. The second is the use of biodegradation to enhance contaminant removal. While SVE was recognized as an efficient source of oxygen for bioremediation as early as 1984, the full development of bioventing did not occur until about 1990. The lack of air in the saturated zone has fostered the development of dual-phase technology. This is the direct use of a high vacuum to dewater and vent saturated soils. Dual-phase technology has allowed SVE to treat contamination below the water table. Finally, the lack of air permeability has led to the development of fracturing systems. Fracturing systems inject pressurized air or water to open channels in the soil, which then allow air to circulate more freely. STATE OF INNOVATIVE REMEDIATION TECHNOLOGY DEVELOPMENT The current state of remediation technology development is relatively rudimentary. That is, technologies are available for treating easily solved contamination problems—mobile and reactive contaminants in permeable and relatively homogeneous geologic settings—but few technologies are available for treating recalcitrant contaminants in complex geologic settings. Figure 3-1 shows a conceptual diagram of where innovation is most needed to improve the performance and reduce the costs of ground water and soil remediation projects. The greatest successes in remediation to date have been in the treatment of petroleum hydrocarbon fuels—gasoline, diesel, and jet fuel—which are generally mobile and biologically reactive and to a lesser extent in the treatment of chlori-
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Innovations in Ground Water and Soil Cleanup: From Concept to Commercialization Figure 3-1 Technology needs for remediation of contaminated ground water and soil. At the left side of the figure, improvements are needed primarily to reduce costs. At the right side, new technologies are needed to solve contamination problems that are currently intractable. nated solvents, which are generally mobile but are less readily biodegraded than petroleum hydrocarbons. The greatest challenge in remediation is in the location and cleanup of contaminant source material. This source material may comprise organic solids, liquids; or vapors; inorganic sludges and other solid-matrix wastes; compounds adsorbed on mineral surfaces; and compounds adsorbed in natural organic matter such as humus. Often, contaminant sources are difficult to locate and delineate because of lack of information about the contaminant spill or disposal history at the site and because contaminant source material may migrate away from where it was originally lost to the environment. Once found, source material may be inaccessible, lying under structures, or at great depth, or in fractured rock. Because of the possibility of continual contaminant release, partial source removal may not result in a proportional increase in ground water quality. The time for source diminution may be excessively long. Further, directing pumped fluids to the region where such fluids are most beneficial may be very difficult because of the problem of preferential flow, which causes fluids to bypass altogether the less permeable regions containing contaminants. A special challenge in the cleanup of source material is in the development of methods to enhance the mobility or reactivity of material that, by its nature, is not particularly mobile or reactive.
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Innovations in Ground Water and Soil Cleanup: From Concept to Commercialization Three Categories of Remediation Technologies Remediation technologies can be divided into three general categories: (1) technologies for solidification, stabilization, and containment; (2) technologies exploiting biological and chemical reactions to destroy or transform the contaminants; and (3) technologies involving separation of the contaminants from the contaminated media, mobilization of the contaminants, and extraction of the contaminants from the subsurface. Box 3-3 provides definitions of the different types of technologies in each of these three categories. Solidification and stabilization processes are directed at decreasing the mobility and/or toxicity of contaminants by reducing contaminant solubility or volatility and medium permeability. Most such techniques have been developed for ex situ treatment of soil contaminated with heavy metals, although a few methods for in situ treatment of relatively shallow contaminated soils are in use. These processes are generally not suited for contaminants located at significant depth or for very volatile or soluble organic contaminants, although some of the methods are now being applied to a limited number of organic contaminants. Containment methods are designed to prevent movement of contaminants away from the zone of contamination by providing a physical or hydraulic barrier. Low-permeability clay and/or geotextile caps and low-permeability slurry walls are fairly standard technology. Combinations of reactive processes with physical containment systems are a new innovation being implemented in the field. Pump-and-treat systems are also often used to hydraulically contain contaminated ground water. Biological and chemical reaction processes use biological or chemical reactions to transform contaminants to innocuous, or at least less harmful, products. Biological processes, known generally as bioremediation, rely on microorganisms to mediate contaminant transformation reactions and degrade the compounds. Many organisms native to soils can use contaminants as sources of carbon and energy for growth. Some organisms (known as aerobes) require oxygen to thrive, while others (known as anaerobes) thrive in oxygen-free environments and use other electron acceptors, such as nitrate, iron, sulfate, and carbon dioxide. Addition of nutrients, moisture, or the appropriate electron acceptors can increase microbial activity and thus enhance the reaction rates. Pretreatment with enzymes or chemical oxidants can make complex chemicals more readily degradable. For in situ bioremediation applications, the primary challenges are largely related to creating the necessary environmental conditions in situ that will cause biodegradation of the contaminants; this includes delivery of the necessary amendments to contaminated locations. Chemical reaction processes are not used as frequently as biological processes. Few chemical reaction processes are available, and even fewer have been tested extensively. However, several technologies are now being tested, as shown in Box 3-3. Reaction processes, whether biological or chemical, are the only processes that can completely destroy organic contaminants. The
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Innovations in Ground Water and Soil Cleanup: From Concept to Commercialization BOX 3-3 A Glossary of Remediation Technologies Stabilization/Solidification and Containment Technologies Asphalt batching. Encapsulates contaminated soil in an asphalt matrix. Volatile organic compounds (VOCs) generally volatilize during the process and are captured and treated in an off-gas system. Biostabilization. An ex situ microbial process to rapidly degrade the bioavailable components (the more volatile and soluble fractions of contaminant mixtures). The process leaves behind a much less mobile and less bioavailable residue. Enhanced sorption. A passive-reactive barrier (see definition below) that creates zones that cause contaminant sorption, either microbiologically (biosorption) or chemically (using surfactant coatings). In situ precipitation/coprecipitation. A passive-reactive barrier (see definition below) that causes the precipitation of a solid (usually carbonate, hydroxide, or sulfide mineral) to maintain a toxic metal in an immobile form. Formation of solid phases is controlled primarily by pH, redox potential, and concentration of other ions. In situ soil mixing. A method of achieving stabilization of contaminated soil in situ. Soil is mixed with stabilizing agents using large augers in successive drillings across a site. Lime addition. A method that decreases permeability of soils by filling interstitial pore spaces and forming weak bonds between soil particles. Heat generated due to hydration can aid in thermal desorption of VOCs. Passive-reactive barriers. Permeable containment barriers that intercept contaminant plumes and remove contaminants from ground water solution using chemical and/or biological reactions within the barrier. Pozzolonic agents. Cement-like materials that form chemical bonds between soil particles and can form chemical bonds with inorganic contaminants, decrease permeability, and prevent access to contaminants. The most common pozzolonic materials are portland cement, fly ash, ground blast furnace slag, and cement kiln dust. Slurry walls, sheet pile walls, and grout walls. Low-permeability barriers designed to prevent contaminant transport in situ. The success of these technologies depends on achievement of a long-lived, low-permeability barrier. Because these walls create hydraulic confinement, fluid must either be allowed to flow around them or be removed from the system and treated if necessary. Alternatively, the barrier wall must contain permeable zones in which reactions can occur. Vitrification. Melting of contaminated soil combined with amendments as needed to form a glass matrix from the soil, either in place (in situ vitrification) or in a treatment unit. Nonvolatile metals and radioactive contaminants become part of the resulting glass block after cooling. Organic contaminants are either destroyed or volatilized by the ex-
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Innovations in Ground Water and Soil Cleanup: From Concept to Commercialization to predict when contaminants are bioavailable, either to microorganisms that can degrade the contaminants or to sensitive human and ecological receptors that may be harmed by the contamination. Information is also needed to determine how biodegradation of hydrophobic organic compounds affects the mobility and toxicity of residuals that remain after active biotreatment. Such information is needed to determine whether contaminants that remain in place but are not bioavailable warrant further remediation. Effectiveness and rates of bioremediation processes, especially those capable of treating organic contaminant mixtures, compounds having low solubilities, strongly sorbed compounds, and compounds resistant to degradation. Although widely studied, the design of bioremediation processes is, in general, empirical. Rate-controlling parameters are largely unknown, and treatment end points are unpredictable, especially for contaminants other than easily degradable petroleum hydrocarbons. Physical, chemical, and biological processes affecting the rate of intrinsic bioremediation. As for engineered bioremediation processes, current scientific knowledge is inadequate to provide accurate predictions of the rate and extent of intrinsic bioremediation, especially for contaminants other than easily degradable petroleum hydrocarbons. Such work should address techniques for predicting the rate of intrinsic bioremediation in advance and identifying suitable monitoring strategies for sites where this approach is appropriate. Factors affecting the performance of solvent-and surfactant-based processes for contaminant remediation. The scientific basis for predicting the performance and kinetics of these processes needs to be improved. Factors related to process performance include hydrologic control of pumped fluids, management and reuse of pumped fluids, doses of solvents and surfactants, effects of residual chemical additives, and heterogeneities in the geologic media. Materials handling for remediation technologies involving mixing and/or moving and processing of large quantities of solids. Handling of large volumes of soil and sludge can pose equipment and materials problems for both in situ stabilization and solidification techniques and ex situ soil treatment systems. For in situ stabilization and solidification techniques, the ability to achieve desired results requires attention to sampling and geostatistical techniques to ensure the thoroughness of treatment. Long-term effectiveness of in situ solidification, stabilization, and containment techniques. Having a scientific basis for determining the life of these systems is essential for long-term protection of public health and the environment. Current understanding of the longevity of solidification, stabilization, and containment techniques is inadequate. Long-term effectiveness of in situ biotic and abiotic processes that decrease the mobility of metals. The effectiveness of novel sorbents for capture of metals needs greater evaluation at the field scale. Soil flushing systems need similar study for metals remediation. Capture of metals by wetlands and other
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Representative terms from entire chapter: