The Role of Bioattenuation in the Management of Aromatic Hydrocarbon Plumes in Aquifers

Ground water scientists have made significant advances in understanding the soil interactions, hydrogeology, fate and transport, and subsurface microbiology of aromatic hydrocarbons (BTEX) in aquifer systems. It is now generally recognized that a major factor responsible for the attenuation and mass reduction of BTEX in plumes is the widespread occurrence of hydrocarbon biodegradation by indigenous soil microorganisms in aquifer material. Most well-studied BTEX plumes that develop from the accidental release of gasoline fuels contain low levels of soluble hydrocarbons (< 1 to 5000 ppb) and have been shown to be spatially confined because of natural biotransformation mechanisms. These in situ processes are controlled by source and aquifer characteristics, permeability, sorption, and geochemical properties of the aquifer. Many laboratory subsoil-ground water microcosms and field studies (10 to 20 C) have demonstrated the rapid biodecay (1 to SO percent/day for microcosms and 0.5 to 1.5 percent/day for plumes) of these aromatic compounds under primarily aerobic conditions (i.e., those with sufficient dissolved oxygen). The ability to implement ground water bioremediation will depend upon our understanding of source control and aquifer recharge effects on the spatial distribution of plumes. In addition, estimating the biodegradation of sorbed BTEX, determining limits and potential for in situ biostimulation of soluble plumes, and establishing data requirements for predictive modeling of natural attenuation will be useful for this remediation technology. The use of these tools to manage ground water quality appears to represent the most practical alternative, particularly for low-risk ground water supplies.     

Chlorinated Solvent Source‐Zone Remediation via ZVI‐Clay Soil Mixing: 1‐Year Results

ZVI‐Clay is an emerging remediation approach that combines zero‐valent iron (ZVI)‐mediated degradation and in situ stabilization of chlorinated solvents. Through use of in situ soil mixing to deliver reagents, reagent‐contaminant contact issues associated with natural subsurface heterogeneity are overcome. This article describes implementation, treatment performance, and reaction kinetics during the first year after application of the ZVI‐Clay remediation approach at Marine Corps Base Camp Lejeune, North Carolina. Primary contaminants included trichloroethylene, 1,1,2,2‐tetrachloroethane, and related natural degradation products. For the field application, 22,900 m³ of soils were treated to an average depth of 7.6 m with 2% ZVI and 3% sodium bentonite (dry weight basis). Performance monitoring included analysis of soil and water samples. After 1 year, total concentrations of chlorinated volatile organic compounds (CVOCs) in soil samples were decreased by site‐wide average and median values of 97% and >99%, respectively. Total CVOC concentrations in groundwater were reduced by average and median values of 81% and >99%, respectively. In several of the soil and groundwater monitoring locations, reductions in total CVOC concentrations of greater than 99.9% were apparent. Further reduction in concentrations of chlorinated solvents is expected with time. Pre‐ and post‐mixing average hydraulic conductivity values were 1.7 × 10^?5 and 5.2 × 10^?8 m/s, respectively, indicating a reduction of about 2.5 orders of magnitude. By achieving simultaneous contaminant mass depletion and hydraulic conductivity reduction, contaminant flux reductions of several orders of magnitude are predicted.     

Laboratory Column Experiments Using Polymer Mats to Remove Selected VOCs, PAHs, and Pesticides from Ground Water

Large-scale column experiments were undertaken to evaluate the potential of polymer mats to remove selected volatile organic compounds, polycyclic aromatic hydrocarbons, and pesticides (atrazine and fenamiphos) from ground water and potentially to act as permeable reactive barriers in contaminated ground water environments. The polymer mats, composed of interwoven silicone (dimethylsiloxane) tubes and purged with air, were installed in 2 m long flow-through columns. The polymer mats proved efficient in physically removing (stripping) benzene and naphthalene from contaminated water. Removal efficiencies for both these compounds from an aqueous phase flowing past a polymer mat were 75% or greater. However, for atrazine and fenamiphos, removal efficiencies were 5% or less, probably as a result of their lower Henry's law constants and possibly lower polymer diffusion coefficients.
These experiments indicate that, at least for relatively volatile compounds, polymer mats can provide a remediation technique for the removal of organic compounds from contaminated water. Application of this technique may be well suited as a longer-term, semipassive strategy to remediate contaminated ground water, using natural ground water flow to deliver contaminated ground water to polymer mats engineered as sorption-stripping barriers.
Additional benefits of this technique may include targeted delivery of gaseous chemical amendments, such as oxygen, to enhance aerobic biodegradation and to further reduce any residual concentrations of contaminants.     

Remediation of Contaminated Ground Water Using Biological Techniques

On-site biological cleanup following spills of biodegradable hazardous organic compounds in lagoon, soil, and ground water environments is a cost-effective technique when proper engineering controls are applied. Biodegradation of hazardous organic contaminants by microorganisms minimizes liability by converting toxic reactants into harmless end products.
Three case histories presented in this paper detail:
• Bench-scale evaluation of the potential for biological remediation in the spill site matrix
• Field implementation of biological treatment techniques.
Cost-effectiveness, minimal disturbance to existing operations, and on-site destruction of spilled contaminants are several of the advantages identified for implementing biodegradation as a technique for spill cleanup and environmental restoration.     

Monitored Natural Attenuation of Contaminants in the Subsurface: Processes

Among the alternatives considered for the remediation of soil and ground water at hazardous wastes sites are the use of natural processes to reduce or remove the contaminants of concern, Under favorable conditions, the use of natural attenuation can result in significant cost savings and compensate for uncertainties encountered in complex subsurface settings. In order to demonstrate that natural processes are effective in reaching established goals it is necessary to determine that transformation processes are taking place at a rate which is protective of human health and the environment, and that these processes will continue for an acceptable period of time.
While chemical transformation, dispersion, dilution, sorption, and volatilization are discussed, aerobic and anaerobic degradation comprise the major processes for the reduction of contaminant mass in the subsurface. In discussing the mechanisms of natural attenuation, chlorinated aliphatics and petroleum hydrocarbons are used as examples because of their significant impact on subsurface contamination and the effect of their physiochemical properties on attenuation processes.     

In Situ Remediation of Jet A in Soil and Ground Water by High Vacuum, Dual Phase Extraction

This report summarizes the initial results of subsurface remediation at Terminal 1, Kenneth International Airport, to remediate soil and ground water contaminated with Jet A fuel. The project was driven and constrained In the const ruction schedule of a major new terminal at the facility. The remediation system used a combination of ground water pumping, air injection, and soil vapor extraction. In the first five months of operation, the combined processes of dewatering, volatilization, and biodegradation removed a total of 36,689 pounds of total volatile and semivolatile organic jet fuel hydrocarbons from subsurface soil and ground water. The. results of this case study have shown that 62 percent of the removal resulted from biodegradation, 21 percent occurred as a result of liquid removal, and 11 percent resulted from the extraction of volatile organic compounds (VOC's).     

In Situ Biorestoration as a Ground Water Remediation Technique

In situ biorestoration, where applicable, is indicated as a potentially very cost-effective and environmentally acceptable remediation technology. Many contaminants in solution in ground water as well as vapors in the unsaturated zone can be completely degraded or transformed into new compounds by naturally occurring indigenous microbial populations. Undoubtedly, thousands of contamination events are remediated naturally before the contamination reaches a point of detection. The need is for methodology to determine when natural biorestoration is occurring, the stage the restoration process is in, whether enhancement of the process is possible or desirable, and what will happen if natural processes are allowed to run their course.
In addition to the nature of the contaminant, several environmental factors are known to influence the capacity of indigenous microbial populations to degrade contaminants. These factors include dissolved oxygen, pH, temperature, oxidation-reduction potential, availability of mineral nutrients, salinity, soil moisture, the concentration of specific pollutants, and the nutritional quality of dissolved organic carbon in the ground water.
Most enhanced in situ bioreclamation techniques available today are variations of hydrocarbon degradation procedures pioneered and patented by Raymond and coworkers at Suntech during the period 1974 to 1978. Nutrients and oxygen are introduced through injection wells and circulated through the contaminated zone by pumping one or more producing wells.
The limiting factor in remediation technology is getting the contaminated subsurface material to the treatment unit or units, or in the case of in situ processes, getting the treatment process to the contaminated material. The key to successful remediation is a thorough understanding of the hydrogeologic and geochemical characteristics of the contaminated area.     

Concurrent Treatment of 1,4‐Dioxane and Chlorinated Aliphatics in a Groundwater Recirculation System Via Aerobic Cometabolism

This research demonstrates that groundwater contaminated by a relatively dilute but persistent concentration of 1,4‐dioxane (1,4‐D), approximately 60 μg/L, and chlorinated aliphatic co‐contaminants (1.4 to 10 μg/L) can be efficiently and reliably treated by in situ aerobic cometabolic biodegradation (ACB). A field trial lasting 265 days was conducted at Operable Unit D at the former McClellan Air Force Base and involved establishing an in situ ACB reactor through amending recirculated groundwater with propane and oxygen. The stimulated indigenous microbial population was able to consistently degrade 1,4‐D to below 3 μg/L while the co‐contaminants trichloroethene (TCE) and 1,2‐dichloroethane (1,2‐DCA) were decreased to below 1 μg/L and 0.18 μg/L, respectively. A stable treatment efficiency of more than 95% removal for 1,4‐D and 1,2‐DCA and of more than 90% removal for TCE was achieved. High treatment efficiencies for 1,4‐D and all co‐contaminants were sustained even without propane and oxygen addition for a 2‐week period.     

The Application of In Situ Air Sparging as an Innovative Soils and Ground Water Remediation Technology

Vapor extraction (soil venting) has been demonstrated to be a successful and cost-effective remediation technology for removing VOCs from the vadose (unsaturated) zone. However, in many cases, seasonal water table fluctuations, drawdown associated with pump-and-treat remediation techniques, and spills involving dense, non-aqueous phase liquids (DNAPLS) create contaminated soil below the water table. Vapor extraction alone is not considered to be an optimal remediation technology to address this type of contamination.
An innovative approach to saturated zone remediation is the use of sparging (injection) wells to inject a hydrocarbon-free gaseous medium (typically air) into the saturated zone below the areas of contamination. The contaminants dissolved in the ground water and sorbed onto soil particles partition into the advective air phase, effectively simulating an in situ air-stripping system. The stripped contaminants are transported in the gas phase to the vadose zone, within the radius of influence of a vapor extraction and vapor treatment system.
In situ air sparging is a complex multifluid phase process, which has been applied successfully in Europe since the mid-1980s. To date, site-specific pilot tests have been used to design air-sparging systems. Research is currently underway to develop better engineering design methodologies for the process. Major design parameters to be considered include contaminant type, gas injection pressures and flow rates, site geology, bubble size, injection interval (areal and vertical) and the equipment specifications. Correct design and operation of this technology has been demonstrated to achieve ground water cleanup of VOC contamination to low part-per-billion levels.     

Cyclodextrin-Enhanced Solubilization of Organic Contaminants with Implications for Aquifer Remediation

Reagents that enhance the aqueous solubility of non-aqueous phase organic liquid (NAPL) contaminants are under investigation for use in enhanced subsurface remediation technologies. Cyclodextrin, a glucose-based molecule, is such a reagent. In this paper, laboratory experiments and numerical model simulations are used to evaluate and understand the potential remediation performance of cyclodextrin. Physical properties of cyclodextrin solutions such as density, viscosity, and NAPL-aqueous inter-facial tension are measured. Our analysis indicates that no serious obstacles exist related to fluid properties that would prevent the use of cyclodextrin solutions for subsurface NAPL remediation. Cyclodextrin-enhanced solubilization for a large suite of typical ground water contaminants is measured in the laboratory, and the results are related to the physicochemical properties of the organic compounds. The most-hydrophobic contaminants experience a larger relative solubility enhancement than the less-hydrophobic contaminants but have lower aqueous-phase apparent solubilities. Numerical model simulations of enhanced-solubilization flushing of NAPL-contaminated soil demonstrate that the more-hydrophilic compounds exhibit the greatest mass-removal rates due to their greater apparent solubilities, and thus are initially more effectively removed from soil by enhanced-solubilization-flushing reagents. However, the relatively more hydrophobic contaminants exhibit a greater improvement in contaminant mass-removal (compared with water flushing) than that exhibited for the relatively hydrophilic contaminants.     

Temperature as a Tool to Evaluate Aerobic Biodegradation in Hydrocarbon Contaminated Soil

This study evaluates the theory, and some practical aspects of using temperature measurements to assess aerobic biodegradation in hydrocarbon contaminated soil. The method provides an easily applicable alternative for quantifying the rate of biodegradation and/or evaluating the performance of in situ remediation systems. The method involves two nonintrusive procedures for measuring vertical temperature profiles down existing monitoring wells; one using a thermistor on a cable for one‐time measurements and the other using compact temperature data loggers deployed for 3‐month to 1‐year period. These vertical temperature profile measurements are used to identify the depth and lateral extent of biodegradation as well as to monitor seasonal temperature changes throughout the year. The basic theory for using temperature measurements to estimate the minimum rate of biodegradation will be developed, and used to evaluate field measurements from sites in California where biodegradation of spilled petroleum hydrocarbons is due to natural processes. Following, temperature data will be used to evaluate the relative rates of biodegradation due to natural processes and soil vapor extraction (SVE) at a former refinery site in the North‐Central United States. The results from this study show that the temperature method can be a simple, cost effective tool for assessing biodegradation in the soil, and optimizing remediation systems at a wide variety of hydrocarbon spill sites.     

Removal of Volatile Organic Compounds in Vertical Flow Filters: Predictions from Reactive Transport Modeling

Vertical flow filters are containers filled with porous medium that are recharged from top and drained at the bottom, and are operated at partly saturated conditions. They have recently been suggested as treatment technology for groundwater containing volatile organic compounds (VOCs). Numerical reactive transport simulations were performed to investigate the relevance of different filter operation modes on biodegradation and/or volatilization of the contaminants and to evaluate the potential limitation of such remediation mean due to volatile emissions. On the basis of the data from a pilot‐scale vertical flow filter intermittently fed with domestic waste water, model predictions on the system’s performance for the treatment of contaminated groundwater were derived. These simulations considered the transport and aerobic degradation of ammonium and two VOCs, benzene and methyl tertiary butyl ether (MTBE). In addition, the advective‐diffusive gas‐phase transport of volatile compounds as well as oxygen was simulated. Model predictions addressed the influence of depth and frequency of the intermittent groundwater injection, degradation rate kinetics, and the composition of the filter material. Simulation results show that for unfavorable operation conditions significant VOC emissions have to be considered and that operation modes limiting VOC emissions may limit aerobic biodegradation. However, a suitable combination of injection depth and composition of the filter material does facilitate high biodegradation rates while only little VOC emissions take place. Using such optimized operation modes would allow using vertical flow filter systems as remediation technology suitable for groundwater contaminated with volatile compounds.     

Effects of Process Control Changes on Aquifer Oxygenation Rates During In Situ Air Sparging in Homogeneous Aquifers

In situ air sparging is used to remediate petroleum fuels and chlorinated solvents present as submerged contaminant source /ones and dissolved contaminant plumes, or to provide barriers to dissolved contaminant plume migration. Contaminant removal occurs through a combination of volatilization and aerobic biodegradation: thus, the performance at any given site depends on the contaminant and oxygen mass transfer rates induced by the air injection. It has been hypothesized that these rates are sensitive to changes in process flow conditions and site lithology, but no data is available to identify trends or the magnitude of the changes. In this work, oxygenation rates were measured for a range of air injection rates, ground water flow rates, and pulsing frequencies using a laboratory-scale two-dimensional physical model constructed to simulate a homogeneous hydrogeologic setting. Experiments were conducted with water having low chemical and biochemical oxygen demand. Results suggest the following: that there is an optimum air injection rate: advective How of ground water can be a significant factor when ground water velocities are > 0.3 m/d: and pulsing the air injection had little effect on the oxygenation rate relative lo the continuous air injection case.     

Thermal Treatment of Eight CVOC Source Zones to Near Nondetect Concentrations

In situ thermal desorption (ISTD) was used for the treatment of eight separate source zones containing chlorinated solvents in a tight loess (silt/clay) above the water table. The source areas were as much as 365 m (1200 feet) apart. A target volume of 38,200 m³ (49,950 cubic yards) of subsurface material to a depth of 9.1 m (30 feet) was treated in a period of 177 days. Energy was delivered through 367 thermal conduction heater borings, and vapors were extracted from 68 vertical vacuum wells. A vapor extraction and capture system, including a surface cover and vertical vacuum wells next to heater borings, provided for effective pneumatic control and capture of the chlorinated volatile organic compound (CVOC) vapors. A central treatment system, based on condensation and granular activated carbon filtration, was used to treat the vapors. Approximately 5675 kg (12,500 pounds) of contaminants was recovered in the extracted vapors. Forty-seven soil samples were used to document remedial performance. Based on these, the concentrations of the target contaminants were reduced to below the target remedial goals in all eight areas, typically with concentrations below 0.01 mg/kg in locations that had had CVOC concentrations higher than 1000 mg/kg. Turn-key costs for the thermal remediation were $3.9 million, and the unit treatment cost, including all utilities, was $103 per cubic meter treated ($79 per cubic yard).     

Bacterial Production Stimulated Across the Zone of Influence of a Ground Water Circulation Well in a BTEX-Contaminated Aquifer

Benzene, toluene, ethylbenzene, and xylene (BTEX) hydrocarbons are typically the most abundant carbon source for bacteria in gasoline-contaminated ground water. In situ bioremediation strategies often involve stimulating bacterial heterotrophic production in an attempt to increase carbon demand of the assemblage. This may, in turn, stimulate biodegradation of contaminant hydrocarbons. In this study, ground water circulation wells (GCWs) were used as an in situ treatment for a fuel-contaminated aquifer to stimulate bacterial production, purportedly by increasing oxygen transfer to the subsurface, circulating limiting nutrients, enhancing bioavailability of hydrocarbons, or by removing metabolically inhibitory volatile organics. Bacterial production, as measured by rates of bacterial protein synthesis, was stimulated across the zone of influence (ZOI) of a series of GCWs. Productivity increased from ∼10² to >10⁵ ng C/L hour across the ZOI, suggesting that treatment stimulated overall biodegradation of carbon sources present in the ground water. However, even if BTEX carbon met all bacterial carbon demand, biodegradation would account for <4.3% of the total estimated BTEX removed from the ground water. Although bacterial productivity measurements alone cannot prove the effectiveness of in situ bioremediation, they can estimate the maximum amount of contaminant that may be biodegraded by a treatment system.     

Evaluation of Mass Flux to and from Ground Water Using a Vertical Flux Model (VFLUX): Application to the Soil Vacuum Extraction Closure Problem

Site closure for soil vacuum extraction (SVE) application typically requires attainment or specified soil concentration standards based on the premise that mass flux from the vadose zone to ground water not result in levels exceeding maximum contaminant levels (MCLs). Unfortunately, realization of MCLs in ground water may not be attainable at many sites. This results in soil remediation efforts that may be in excess of what is necessary for future protection of ground water and soil remediation goals which often cannot be achieved within a reasonable time period. Soil venting practitioners have attempted to circumvent these problems by basing closure on some predefined percent total mass removal, or an approach to a vapor concentration asymptote. These approaches, however, are subjective and influenced by venting design. We propose an alternative strategy based on evaluation of five components: (1) site characterization, (2) design. (3) performance monitoring, (4) rule-limited vapor transport, and (5) mass flux to and from ground water. Demonstration of closure is dependent on satisfactory assessment of all five components. The focus of this paper is to support mass flux evaluation. We present a plan based on monitoring of three subsurface zones and develop an analytical one-dimensional vertical flux model we term VFLUX. VFLUX is a significant improvement over the well-known numerical one-dimensional model. VLEACH, which is often used for estimation of mass flux to ground water, because it allows for the presence of nonaqueous phase liquids (NAPLs) in soil, degradation, and a lime-dependent boundary condition at the water table inter-face. The time-dependent boundary condition is the center-piece of our mass flux approach because it dynamically links performance of ground water remediation lo SVE closure. Progress or lack of progress in ground water remediation results in either increasingly or decreasingly stringent closure requirements, respectively.     

A Study of Long-Term MTBE Attenuation in the Borden Aquifer, Ontario, Canada

In 1988 and 1989, a natural gradient tracer test was performed in the shallow, aerobic and aquifer at Canadian Forces Base (CFB) Borden. A mixture of ground water containing dissolved oxygenated gasoline was injected below the water table along with chloride (Cl-) as a conservative tracer. The migration of BTEX, MTBE, and Cl was monitored in detail for 16 moths. The mass of BTEX compounds in the plume diminished significantly with time due to intrinsic aerobic biodegradation, while MTBE showed only a small decrease in mass over the 16-month period. In 1995/96, a comprehensive ground water sampling program was undertaken to define the mass of MTBE still present in the aquifer. Since the plume had migrated into an unmonitored section of the Borden Aquifer, numerical modeling and geostatistical methods were applied to define an optimal sampling grid and to improve the level of confidence in the results. A drive point profiling system was used to obtain ground water samples. Numerical modeling with no consideration of degradation pedicted maximum concentrations in excess of 3000 μg/L; field sampling found maximum concentrations of less than 200 μg/L. A mass balance for the remaining MTBE mass in the aquifer eight years after injection showed that only 3% of the original mass remained. Sorption, volatilization, a biotic degradation, and plant uptake are not considered significant attenuation processes for the field conditions. Therefore, we suggest that biodegradation may have played a major role in the attenuation of MTBE within the Borden Aquifer.     

A Modified Radial Diagram Approach for Evaluating Natural Attenuation Trends for Chlorinated Solvents and Inorganic Redox Indicators

Selection of monitored natural attenuation as a ground water remedy requires that sound scientific documentation clearly illustrating the effectiveness of this remedial alternative be presented to regulatory agencies and concerned citizens. An innovative radial diagram approach is applied to illustrate natural attenuation trends for total benzene, toluene, ethylbenzene, and xylenes (BTEX) and chlorinated ethenes at a former fire training area at Pittsburgh Air Force Base, New York. A BTEX-CAH (chlorinated aliphatic hydrocarbons) radial diagram map shows that concentrations of site contaminants are generally decreasing along the primary flowpath downgradient from the source area. This radial diagram map also suggests that there is a spatial correlation between decreasing CAH parent compound concentrations and increasing or stable daughter product concentrations. This provides secondary evidence of intrinsic biodegradation of TCE downgradient from the source area. A SEQUENCE-Redox™ map suggests that there is a spatial correlation between trends in electron acceptor and metabolic byproduct concentrations, and the decline in total BTEX concentrations downgradient from the source area. This correlation provides secondary evidence for the intrinsic biodegradation of total BTEX in the aquifer. This study demonstrates that radial diagram visual aids can provide a clear and efficient approach for documenting natural attenuation lines of evidence, as an alternative or a complement to using multiple contour maps, tabulated data, or log-linear plots.     

Enhanced Degradation of Dissolved Benzene and Toluene Using a Solid Oxygen-Releasing Compound

A field lest to evaluate the applicability of an oxygon-releasing compound (ORC) to the rernediation of ground water contaminated with benzone and toluene was conducted in the Borden Aquifer in Ontario. Canada. Benzene and toluene were injected as organic substrates to represent BTEX compounds, bromide was used as a tracer, and nitrate was added to avoid nitrate-limited conditions.
The fate of the solutes was monitored along four lines of monitoring points and wells. Two lines studied the behavior of the solutes upgradient and downgradient of two large-diameter well screens filled with briquets containing ORC and briquets without ORC. One line was used to study the solute behavior upgradient and downgradient of columns of ORC powder placed directly in the saturated zone. The remaining line was a control.
The results indicate that ORC in both briquet and powder form can release significant amounts of oxygen to conlaminated ground water passing by it. In the formulation used in this work, oxygen release persisted for at least 10 weeks. Furthemiore, the study indicates that the enhancement of the available dissolved oxygen content of at least 4 mg/L each of the ground water by ORC can support biodegradation of benzene and toluene dissolved in ground water. Such concentrations are typical of those encountered at sites contaminated with petroleum hydrocarbons; therefore, these results suggest that there is promise for ORC to enhance in situ biodegradation of BTKX contaminants at such sites using passive (nonpumping) systems to contact the contaminated ground water with the oxygen source.     

Engineering and hydrogeological problems associated with in situ treatment

Abstract

Most organic materials that contaminate soil and the subsurface environment are readily degraded by natural biological processes. To this degree, in situ bioremediation can be thought of as a highly successful purification process. However, some organic molecules are naturally refractory to biodegradation, or other environmental factors induce molecular recalcitrance such as the absence of a proper microbial population or the presence of unsuitable environmental conditions. Examples of recalcitrant groundwater contaminants are soluble components of petroleum hydrocarbons (BTEX) and chlorinated aliphatic hydrocarbons (CAHs). Organic recalcitrance may be changed through introduction of degrading populations of microorganisms or by changing the environmental conditions through introduction of nutrients or other chemicals. The most significant engineering deficiency in in situ bioremediation is the absence of proven methods to introduce such materials into the subsurface environment for efficient mixing with microorganisms and the contaminants of concern.