DyeLIF™: A New Direct‐Push Laser‐Induced Fluorescence Sensor System for Chlorinated Solvent DNAPL and Other Non‐Naturally Fluorescing NAPLs

DyeLIF? is a new version of laser‐induced fluorescence (LIF) for high‐resolution three‐dimensional subsurface mapping of nonaqueous phase liquids (NAPLs) in the subsurface. DyeLIF eliminates the requirement that the NAPL contains native fluorophores (such as those that occur in compounds like polynuclear aromatic hydrocarbons [PAHs]) and can therefore be used to detect chlorinated solvents and other nonfluorescing NAPLs that had previously been undetectable with conventional LIF tools. With DyeLIF, an aqueous solution of water and nontoxic hydrophobic dye is continuously injected ahead of the sapphire detection window while the LIF probe is being advanced in the subsurface. If soil containing NAPL is penetrated, the injected dye solvates into the NAPL within a few milliseconds, creating strong fluorescence that is transmitted via fiber‐optic filaments to aboveground optical sensors. A detailed field evaluation of the novel DyeLIF technology was performed at a contaminated industrial site in Lowell, Massachusetts, USA where chlorinated solvent dense nonaqueous phase liquid (DNAPL) persists below the water table in sandy sediments. Continuously cored boreholes were drilled adjacent to 5 of 30 DyeLIF probes that were advanced at that site. The cores were subsampled in high resolution to generate discrete‐depth soil samples as splits at the same depths where DNAPL was detected in the colocated DyeLIF probes. The cores were analyzed above ground using (1) colorimetric screening using hydrophobic dye tests, (2) laboratory extraction and quantitative chemical analysis, (3) “Benchtop” DyeLIF, and (4) volumetric moisture content. Correlation between DyeLIF and aboveground analyses of the soil cores was excellent: 98% agreement with positive DNAPL detections in samples where DNAPL pore saturations were >0.7% (based on quantitative soil analyses) and the ex situ tests. DyeLIF produced the equivalent of one aboveground colorimetric dye test every 0.2 inch (0.5 cm) of probing. With average daily probing of 395 linear feet (120.4 m), this was the equivalent of 12,039 discrete‐depth colorimetric dye tests/day. Because DyeLIF is an in situ measurement, there are no issues with soil core recovery like there would be for conventional ex situ colorimetric dye tests and 100% characterization of the probed intervals is achieved. Tracking the injection rate and pressure of the dye solution provides simultaneous data regarding relative soil permeability, similar to other direct push (DP) hydraulic profiling tools. Conventional LIF is considered the premier DP tool to identify and map NAPL containing PAHs in the subsurface or confirm its absence. While chlorinated solvent DNAPLs at some field sites contain impurities (e.g., solvated greases or oils) that make them detectable with conventional LIF techniques, at other sites, the DNAPL cannot be detected with conventional LIF. At such sites, the injection of a hydrophobic dye ahead of the sapphire window with the DyeLIF system now makes the LIF technology applicable to the many types of NAPLs that were previously invisible using conventional LIF techniques.     

DNAPL Characterization Methods and Approaches, Part 1: Performance Comparisons

Contamination from the use of chlorinated solvents, often classified as dense nonaqueous phase liquids (DNAPLs) when in an undissolved state, represents an environmental challenge with global implications. Mass-transfer limitations due to rate-limited dissolution can lead to long-term aquifer persistence for even small volumetric fractions. The identification of DNAPL source zones located beneath the water table is critical to ultimately achieve site remediation and aquifer restoration. This paper provides a comparison of the advantages and disadvantages of many of the methods being used for detecting and delineating DNAPL contaminant source zones. The objective is to determine which options are best to pursue based on site characteristics, method performance, and method costs. DNAPL characterization methods are grouped into approaches, which include site preparation, characterization, and data-processing activities necessary to design an effective remediation system. We compare the different approaches based on the level of chemical and hydrogeologic resolution, and the need for additional data requirements. Our findings can be used to assist with selection of appropriate site remediation management options.     

High-Resolution Characterization of a Chlorinated Solvent Impacted Aquifer Using a Passive Profiler

A direct-drive high-resolution passive profiler (HRPP) was developed to quantify and delineate concentrations of chlorinated volatile organic compounds (CVOCs), geochemical indicators and CVOC-degrading microorganisms/genes, as well as to perform compound-specific stable isotope analysis (CSIA) of CVOCs and estimate interstitial velocity at <30-cm resolution. The profilers can be coupled together to provide a continuous sample interval and advanced to depths up to approximately 9 m below-ground surface (bgs) within saturated media where direct-push techniques are feasible. The HRPP was field tested in a previous dense nonaqueous phase liquid (DNAPL) source zone at the former Naval Air Station in Alameda, CA. HRPP data sets were compared to the following traditional groundwater data sets: CVOC and anion concentrations in standard and multilevel monitoring well water samples, CVOC concentrations in soil core samples, qualitative contaminant profiles delineated with a membrane interface probe (MIP), microbial community and CSIA profiles from Bio-Traps® deployed in wells, groundwater velocity from passive flux meters (PFMs), lithologic profiles correlated with MIP electrical conductivity (EC), and velocity estimates based on permeability profiles measured with a Geoprobe hydraulic profiling tool (HPT). In some cases, the HRPP data were equivalent to traditional techniques and, in other cases, the HRPP data were more representative of local variability rather than bulk aquifer conditions. Overall the results support the use of the HRPP to provide high-resolution data on concentrations, velocity, and microbial activity in temporary direct-push deployments without well installation, providing a new tool to better assess source zones and contaminated groundwater plumes, even in low permeability media, and to increase the fidelity of site transport models.     

Microtopographical and hydrophysical controls on subsurface flow and solute transport: A continuous solute release experiment in a subarctic bog

Resource extraction and transportation activities in subarctic Canada can result in the unintentional release of contaminants into the surrounding peatlands. In the event of a release, a thorough understanding of solute transport within the saturated zone is necessary to predict plume fate and the potential impacts on peatland ecosystems. To better characterize contaminant transport in these systems, approximately 13,000 L/day of sodium chloride tracer (200 mg/L) was released into a bog in the James Bay Lowland. The tracer was pumped into a fully penetrating well (1.5 m) between July 5 and August 18, 2015. Horizontal and vertical plume development was measured via in situ specific conductance and water table depth from an adaptive monitoring network. Over the spill period, the bulk of the plume travelled a lateral distance of 100 m in the direction of the slight regional groundwater and topographical slope. The plume shape was irregular and followed the hollows, indicating preferential flow paths due to the site microtopography. Saturated transport of the tracer occurred primarily at ~25 cm below ground surface (bgs), and at a discontinuous high hydraulic conductivity layer ~125 cm bgs due to a complex and heterogeneous vertical hydraulic conductivity profile. Plume measurement was confounded by a large amount of precipitation (233 mm over the study period) that temporarily diluted the tracer in the highly conductive upper peat layer. Longitudinal solute advection can be approximated using local water table information (i.e., depth and gradient); microtopography; and meteorological conditions. Vertical distribution of solute within the peat profile is far more complex due to the heterogeneous subsurface; characterization would be aided by a detailed understanding of the site‐specific peat profile; the degree of decomposition; and the type of contaminant (e.g., reactive/nonreactive). The results of this research highlight the difficulty of tracking a contaminant spill in bogs and provide a benchmark for the characterization of the short‐term fate of a plume in these complex systems.     

Bioremediation Management Reduces Mass Discharge at a Chlorinated DNAPL Site

Adaptive site management and aggressive bioremediation in the source zone of a complex chlorinated dense nonaqueous phase liquid (DNAPL) site reduced total chlorinated hydrocarbon mass discharge by nearly 80%. Successful anaerobic bioremediation of chlorinated hydrocarbons can be impaired by inadequate concentrations of electron donors, competing electron acceptors, specific inhibitors such as chloroform, and potentially by high contaminant concentrations associated with residual DNAPL. At the study site, the fractured bedrock aquifer was impacted by a mixture of chlorinated solvents and associated daughter products. Concentrations of 1,1,2,2‐tetrachloroethane (1,1,2,2‐TeCA), 1,1,2‐trichloroethane (1,1,2‐TCA), and 1,2‐dichloroethane (1,2‐DCA) were on the order of 100 to 1000 mg/L. Chloroform was present as a co‐contaminant and background sulfate concentrations were approximately 400 mg/L. Following propylene glycol injections, concentrations of organohalide‐respiring bacteria including Dehalococcoides and Dehalogenimonas spp. increased by two to three orders of magnitude across most of the source area. Statistical analysis indicated that reaching volatile fatty acid concentrations greater than 1000 mg/L and depleting sulfate to concentrations less than 50 mg/L were required to achieve a Dehalococcoides concentration greater than the 10⁴ cells/mL recommended for generally effective reductive dechlorination. In a limited area, chloroform concentrations greater than 5 mg/L inhibited growth of Dehalococcoides populations despite the availability of electron donor and otherwise appropriate geochemical conditions. After implementing a groundwater recirculation system targeting the inhibited area, chloroform concentrations decreased permitting significant increases in concentrations of Dehalococcoides and vinyl chloride reductase gene copies.     

Cryogenic Core Collection (C3) from Unconsolidated Subsurface Media

We evaluated tools and methods for in situ freezing of cores in unconsolidated subsurface media. Our approach, referred to as cryogenic core collection (C₃), has key aspects that include downhole circulation of liquid nitrogen (LN) via a cooling system, strategic use of thermal insulation to focus cooling into the core, and controlling LN back pressure to optimize cooling. Two cooling systems (copper coil and dual‐wall cylinder) are described. For both systems, the time to freeze a single 2.5‐foot (76‐cm) long by 2.5‐inch (63‐mm) diameter core is 5 to 7 min. Frozen core collection rates of about 30 feet/day (10 m/day) were achieved at two field sites, one impacted by petroleum‐based light nonaqueous phase liquids (LNAPLs) and the other by chlorinated solvents. Merits of C₃ include (1) improved core recovery, (2) potential control of flowing sand, and (3) improved preservation of critical sediment attributes. Development of the C₃ method creates novel opportunities to characterize sediment with respect to physical, chemical, and biological properties. For example, we were able to resolve water, LNAPL, and gas saturations above and below the water table. By eliminating drainage of water, gas and LNAPL saturations in the range of 6 to 23% and 1 to 3% of pore space, respectively, were measured in LNAPL‐impacted intervals below the water table.     

ISCO for Groundwater Remediation: Analysis of Field Applications and Performance

A critical analysis of in situ chemical oxidation (ISCO) projects was performed to characterize situations in which ISCO is being implemented, how design and operating parameters are typically employed, and to determine the performance results being achieved. This research involved design of a database, acquisition and review of ISCO project information, population of the database, and analyses of the database using statistical methods. Based on 242 ISCO projects included in the database, ISCO has been used to treat a variety of contaminants; however, chlorinated solvents are by far the most common. ISCO has been implemented at sites with varied subsurface conditions with vertical injection wells and direct push probes being the most common delivery methods. ISCO has met and maintained concentrations below maximum contaminant levels (MCLs), although not at any sites where dense nonaqueous phase liquids (DNAPL) were presumed to be present. Alternative cleanup levels and mass reduction goals have also been attempted, and these less stringent goals are met with greater frequency than MCLs. The use of pilot testing is beneficial in heterogeneous geologic media, but not so in homogeneous media. ISCO projects cost $220,000 on average, and cost on average $94/yd³ of target treatment zone. ISCO costs vary widely based on the size of the treatment zone, the presence of DNAPL, and the oxidant delivery method. No case studies were encountered in which ISCO resulted in permanent reductions to microbial populations or sustained increases in metal concentrations in groundwater at the ISCO-treated site.     

Integrity of Clay Till Aquitards to DNAPL Migration: Assessment Using Current and Emerging Characterization Tools

Field investigations were carried out to determine the occurrence of tetrachloroethene (PCE) dense nonaqueous phase liquid (DNAPL), the source zone architecture and the aquitard integrity at a 30‐ to 50‐year old DNAPL release site. The DNAPL source zone is located in the clay till unit overlying a limestone aquifer. The DNAPL source zone architecture was investigated through a multiple‐lines‐of‐evidence approach using various characterization tools; the most favorable combination of tools for the DNAPL characterization was geophysical investigations, membrane interface probe, core subsampling with quantification of chlorinated solvents, hydrophobic dye test with Sudan IV, and Flexible Liner Underground Technologies (FLUTe) NAPL liners with activated carbon felt (FACT). While the occurrence of DNAPL was best determined by quantification of chlorinated solvents in soil samples supported by the hydrophobic dye tests (Sudan IV and NAPL FLUTe), the conceptual understanding of source zone architecture was greatly assisted by the indirect continuous characterization tools. Although mobile or high residual DNAPL (S _t > 1%) only occurred in 11% of the source zone samples (intact cores), they comprised 86% of the total PCE mass. The dataset, and associated data analysis, supported vertical migration of DNAPL through fractures in the upper part of the clay till, horizontal migration along high permeability features around the redox boundary in the clay till, and to some extent vertical migration through the fractures in the reduced part of the clay till aquitard to the underlying limestone aquifer. The aquitard integrity to DNAPL migration was found to be compromised at a thickness of reduced clay till of less than 2 m.     

World's Largest In Situ Thermal Desorption Project: Challenges and Solutions

This paper presents the largest In Situ Thermal Desorption (ISTD) project completed to date. The redevelopment of a former aerospace manufacturing facility adjacent to a commercial airport was the main driver, requiring relatively rapid reduction of several chlorinated volatile organic compounds (CVOC) in a 3.2‐acre source zone. The source zone was divided into four quadrants with differing treatment depths, heated simultaneously using a total of 907 thermal conduction heater wells. Five different depths were selected across the area, according to the depth of contaminant impact. Prior to implementation, a risk and optimization study led to placement of a vertical sheet‐pile wall around the treatment zone to minimize groundwater flow, and a pilot test of a novel direct‐drive method for installation of the heater casings. Because of a shallow water table, a layer of clean fill was placed over the treatment zone, and partial dewatering was necessary prior to heating. A network of vertical multiphase extraction wells and horizontal vapor extraction wells was used to establish hydraulic and pneumatic control and to capture the contaminants. The site was split into four decision units, each with a rigorous soil sampling program which included collecting a total of 270 confirmatory soil samples from locations with the highest pretreatment CVOC concentrations requiring reduction to below 1 mg/kg for each contaminant. Temperature monitoring and mass removal trends were used to trigger the sampling events. Eventually, a small area near the center of the site required the installation of four additional heaters before the soil goals were reached after 238 days of heating. The total energy usage for heating and treating the source area was 23 million kWh—slightly lower than the estimated 26.5 million kWh. Actual energy losses and the energy removal associated with the extracted steam were lower than anticipated. An estimated 13,400 kg (29,800 lbs) of CVOC mass was removed, and all soil goals were met. This paper presents the challenges associated with a project of this scale and describes the solutions to successfully complete the ISTD remedy.     

DNAPL Characterization Methods and Approaches, Part 2: Cost Comparisons

Contamination from the use of chlorinated solvents, often classified as dense nonaqueous phase liquids (DNAPLs) when in an undissolved state, pose environmental threats to ground water resources worldwide. DNAPL site characterization method performance comparisons are presented in a companion paper (Kram et al. 2001). This study compares the costs for implementing various characterization approaches using synthetic unit model scenarios (UMSs), each with particular physical characteristics. Unit costs and assumptions related to labor, equipment, and consumables are applied to determine costs associated with each approach for various UMSs. In general, the direct-push sensor systems provide cost-effective characterization information in soils that are penetrable with relatively shallow (less than 10 to 15 m) water tables. For sites with impenetrable lithology using direct-push techniques, the Ribbon NAPL Sampler Flexible Liner Underground Technologies Everting (FLUTe) membrane appears to be the most cost-effective approach. For all scenarios studied, partitioning interwell tracer tests (PITTs) are the most expensive approach due to the extensive pre-and post-PITT requirements. However, the PITT is capable of providing useful additional information, such as approximate DNAPL saturation, which is not generally available from any of the other approaches included in this comparison.     

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.     

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).     

Influence of Shallow Geology on Volatile Organic Chemical Attenuation from Groundwater to Deep Soil Gas

Vapor intrusion pathway evaluations commonly begin with a comparison of volatile organic chemical (VOC) concentrations in groundwater to generic, or Tier 1, screening levels. These screening levels are typically quite low reflecting both a desired level of conservatism in a generic risk screening process as well as limitations in understanding of physical and chemical processes that impact vapor migration in the subsurface. To study the latter issue, we have collected detailed soil gas and groundwater vertical concentration profiles and evaluated soil characteristics at seven different sites overlying chlorinated solvent contaminant plumes. The goal of the study was to evaluate soil characteristics and their impacts on VOC attenuation from groundwater to deep soil gas (i.e., soil gas in the unsaturated zone within 2 feet of the water table). The study results suggest that generic screening levels can be adjusted by a factor of 100× at sites with fine‐grained soils above the water table, as identified by visual observations or soil air permeability measurements. For these fine‐grained soil sites, the upward‐adjusted screening levels maintain a level of conservatism while potentially eliminating the need for vapor intrusion investigations at sites that may not meet generic screening criteria.     

Bioaugmentation in a Well‐Characterized Fractured Rock DNAPL Source Area

A field demonstration was performed at Edwards Air Force Base to assess bioaugmentation for treatment of a well‐characterized tetrachloroethene (PCE) dense nonaqueous phase liquid (DNAPL) source area in fractured rock. Groundwater recirculation was employed to deliver remedial amendments, including bacteria, to facilitate reductive dechlorination and enhance DNAPL dissolution. An active treatment period of 9 months was followed by a 10‐month posttreatment rebound evaluation. Dechlorination daughter products were observed in both the shallow and deep fracture zones following treatment. In the shallow fracture zone, the calculated DNAPL mass removed was approximately equal to the DNAPL mass estimated using partitioning tracer testing, and no rebound in chlorinated ethenes or ethene was observed during the posttreatment period. A maximum DNAPL dissolution enhancement factor of 5 was observed in the shallow fracture zone. In the deep fracture zone, only approximately 45% of the DNAPL mass—as estimated via partitioning tracer testing—was removed and rebound in the total molar chlorinated ethenes + ethene was observed. The difference in behavior between the shallow and deep fracture zones was attributed to DNAPL architecture and the fracture flow field.     

The use of GPR and VES in delineating a contamination plume in a landfill site: a case study in SE Brazil

This paper presents the results of the application of the Ground Penetrating Radar (GPR) method, or Georadar, in outlining a zone of contamination due to solid residues at the waste burial site of Rio Claro in the state of São Paulo, SE Brazil. A total of eight GPR profiles with 50- and 100-MHz antennae were surveyed. Six profiles were located within the landfill site and the remaining two were outside. The main objective of the GPR survey was to evaluate the side extension of contamination. A Vertical Electric Sounding (VES) survey was performed at four points within the site in order to investigate the vertical extent of the contamination plume and to define the bottom of the landfill. Two additional VESs were done outside the landfill with the purpose of determining the top of the ground water table and the geoelectric stratigraphy of the background. From the interpretation of the GPR profiles, it was possible to locate the top of the contamination plume and to infer that it was migrating laterally beyond the limits of the waste disposal site. This was observed along the profile situated close to the highway SP-127, which was about 20 m from the limit of the site. The signature of the contaminant appears as a discontinuous reflector that is believed to be a shallow ground water table. The discontinuity is marked by a shadow zone, which is characteristic of conductive contaminant residues. The contamination did not move far enough to reach a sugar cane plantation located at approximately 100 m from the border of the site. In the regions free from contamination, the ground water table was mapped at approximately 10 m of depth, and it was characterized by a strong and continuous reflector. The radar signal penetrated deep enough and enabled the identification of a second reflector at approximately 14 m deep, interpreted as the contact between the Rio Claro and the Corumbataí formations. The contact is marked by the presence of gravel characterized by ferruginous concretes, which cause the strong amplitude reflection in the GPR profile. Within the landfill site, the quantitative interpretation of the VES results showed the contamination zone. The base of the landfill varies between 11 and 15 m deep. Outside the landfill site, the VES results showed no indication of contamination and allowed the determination of the top of the ground water table and the contact between the Rio Claro and the Corumbataí formations. The results of GPR and VES showed a good agreement and the integrated interpretations were supported by local geology and information from several boreholes, about 17 m depth, on average. The bottom of the landfill reaches a maximum of 14.5 m depth.     

Vitamin B12 and Reduced Titanium for Remediation of Residual Chlorinated Solvents: Field Experiment

A first pilot-scale field experiment using vitamin B₁₂ and reduced titanium was conducted in an in situ vertical circulation column at CFB Borden. The objective of the experiment was to test the applicability of the technology for restoring aquifer source zones contaminated by chlorinated solvents—tetrachloroethene (PCE) and 1,1,1-trichloroethane (1,1,1-TCA)—in a mixture of dense nonaqueous phase liquids (DNAPLs). Vitamin B₁₂ promotes the reductive dechlorination of chlorinated organics. A highly reducing and slightly alkaline environment must be maintained (Eh < - 480 mV and 7 < pH < 9) to maximize the rate of degradation. In this field test, PCE and 1,1,1-TCA degraded to a limited extent under experimental conditions, with 1,1,1-TCA degrading more readily. Indigenous bacteria were found to metabolize citrate, which caused titanium to precipitate, limiting degradation. The addition of glucose at the end of a second field season effectively limited citrate degradation and helped recover the optimal redox potential by keeping reduced titanium in solution. A laboratory column was used to confirm field results. The column also produced a significant biomass, which provided an additional source of organic carbon onto which the solvents sorbed.     

Impact of Recharge Through Residual Oil Upon Sampling of Underlying Ground Water

At an aviation gasoline spill site in Traverse City, Michigan, historical records indicate a positive correlation between significant rainfall events and increased concentrations of slightly soluble organic compounds in the monitoring wells of the site. To investigate the recharge effect on ground water quality due to infiltrating, water percolating past residual oil and into the saturated zone, an in situ infiltration experiment was performed at the site. Sampling cones were set at various depths below a circular test area, 13 feet (4 meters) in diameter. Rainfall was simulated by sprinkling the test area at a rate sufficiently low to prevent runoff. The sampling cones for soil-gas and ground water quality were installed in the unsaturated and saturated zones to observe the effects of the recharge process. At the time of the test, the water table was below the residual oil layer. The responses of the soil-gas and ground water quality were monitored during the recharge and drainage periods, which resulted from the sprinkling.
Infiltrated water was determined to have transported organic constituents of the residual oil, specifically benzene, toluene, ethylbenzene, and ortho-xylene (BTEX), into the ground water beneath the water table, elevating the aqueous concentrations of these constituents in the saturated zone. Soil-gas concentrations of the organic compounds in the unsaturated zone increased with depth and time after the commencement of infiltration. Reaeration of the unconfined aquifer via the infiltrated water was observed. It is concluded that water quality measurements are directly coupled to recharge events for the sandy type of aquifer with an overlying oil phase, which was studied in this work. Ground water sampling strategies and data analysis need to reflect the effect of recharge from precipitation on shallow, unconfined aquifers where an oil phase may be present.     

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.     

Effects of In Situ Remediation Using Oxidants or Surfactants on Subsurface Organic Matter and Sorption of Trichloroethene

In situ remediation technologies have the potential to alter subsurface properties such as natural organic matter (NOM) content or character, which could affect the organic carbon‐water partitioning behavior of chlorinated organic solvents, including dense nonaqueous phase liquids (DNAPLs). Laboratory experiments were completed to determine the nature and extent of changes in the partitioning behavior of trichloroethene (TCE) caused by in situ chemical oxidation or in situ surfactant flushing. Sandy porous media were obtained from the subsurface at a site in Orlando, Florida. Experiments were run using soil slurries in zero‐headspace reactors (ZHRs) following a factorial design to study the effects of porous media properties (sand vs. loamy sand with different total organic carbon [TOC] contents), TCE concentration (DNAPL presence or absence), and remediation agent type (potassium permanganate vs. activated sodium persulfate, Dowfax 8390 vs. Tween 80). Results revealed that the fraction of organic carbon (f_oc) of porous media after treatment by oxidants or surfactants was higher or lower relative to that in the untreated media controls. Isotherm experiments were run using the treated and control media to measure the distribution coefficient (K_d) of TCE. Organic carbon‐water partitioning coefficient values (K_oc) calculated from the experimental data revealed that K_oc values for TCE in the porous media were altered via treatment using oxidants and surfactants. This alteration can affect the validity of estimates of contaminant mass remaining after remediation. Thus, potential changes in partitioning behavior should be considered to help avoid decision errors when judging the effectiveness of an in situ remediation technology.     

Comparison of Line-Drive and Push-Pull Flushing Schemes

The performance of cyclodextrin (CD)‐enhanced push‐pull (PP) and line‐drive (LD) approaches to remediation of a site contaminated with a multicomponent dense nonaqueous phase liquid (DNAPL) present in a surficial sandy aquifer was evaluated in this field study. The treatment techniques were compared to each other and to the projected performance of a conventional water‐flushing system. Performance was assessed based on contaminant mass removed per unit volume of extraction solution and per unit time of operation. As expected, the CD‐enhanced LD and PP approaches to remediation were more efficient than conventional flushing with water. Between the two techniques, the PP approach performed 1.5 to 2 times better than the LD approach, particularly for higher DNAPL saturation of the source zone. This result suggests that forcing the flushing solution directly into and through the DNAPL source zone minimized flow bypassing and consequently resulted in a more efficient transfer of contaminant mass between the DNAPL phase and the flushing solution. Nonuniform treatment zone contaminant concentrations and changes in contaminant composition influenced the treatment performances, but these effects were small and still permitted the comparison of successive tests. Although CD was used as the solubility‐enhancing flushing agent in this study, it is likely that the results can be transferred to other chemically enhanced flushing technologies that use, for example, surfactants or alcohols.