Soil-Gas Surveying for Subsurface Gasoline Contamination Using Total Organic Vapor Detection Instruments Part I. Theory and Laboratory Experimentation

Factors influencing the response of total organic vapor detection instruments used in soil-gas surveying for subsurface gasoline leakage were investigated through performing theoretical assessments and laboratory experiments. Theoretical assessments indicate that total organic vapor measurements will depend on response conditions and the relative concentration of constituents in soil gas, in addition to absolute constituent levels. Laboratory tests conducted using flame ionization, photoionization and explosimeter devices indicated that conditions influencing their responses included instrument flow rate and soil-air permeability when performing direct-probe sampling; the linear range of the instrument; the multicomponent nature of gasoline vapors; and levels of oxygen, nitrogen, carbon dioxide and relative humidity in soil air. If an instrument's response to these conditions is not taken into account, survey results may be misleading. To circumvent adverse instrument responses, a serial dilution technique is presented.     

Behavior of gasoline pools following a denatured ethanol spill

In 1999, approximately 72 m3 of denatured fuel-grade ethanol spilled at a bulk fuel terminal that had existing contamination within the subsurface. An unanticipated increase in the measured depth of the light nonaqueous phase liquid (LNAPL) was observed in nearby monitoring wells following the spill. This paper presents results of a laboratory analysis designed to understand the apparent increase in LNAPL mobility at this site. The two-dimensional stainless steel and glass tank allowed visual assessment of the potential effects that the addition of denatured ethanol may have on a site with pre-existing gasoline contamination. Digital images of gasoline and ethanol spill experiments were analyzed for changes in the characteristics of the existing gasoline pool and residual gasoline saturation in the unsaturated zone. Reductions in the surface and interfacial tensions resulted in significant changes in the size, shape, and saturation of the gasoline pool after the addition of ethanol to the system. The final gasoline pool occupied a smaller area and had a higher saturation. In addition, some smearing of the gasoline into the saturated zone occurred as the capillary fringe was depressed.     

Vertical Screening Distance Criteria to Evaluate Vapor Intrusion Risk from 1,2-Dichloroethane (1,2-DCA)

Vapor intrusion (VI) involves migration of volatile contaminants from subsurface through unsaturated soil into overlying buildings. In 2015, the US EPA recommended an approach for screening VI risks associated with gasoline releases from underground storage tank (UST) sites. Additional assessment of the VI risk from petroleum hydrocarbons was deemed unnecessary for buildings separated from vapor sources by more than recommended vertical screening distances. However, these vertical screening distances did not apply to potential VI risks associated with releases of former leaded gasoline containing 1,2-dichloroethane (1,2-DCA), because of a lack of empirical data on the attenuation of 1,2-DCA in soil gas. This study empirically evaluated 144 paired measurements of 1,2-DCA concentrations in soil gas and groundwater collected at 47 petroleum UST sites combined with BioVapor modeling. This included (1) assessing the frequency of 1,2-DCA detections in soil gas below 10⁻⁶ risk-based screening levels at different vertical separation distances and (2) comparing the US EPA recommended vertical screening distances with those predicted by BioVapor modeling. Vertical screening distances were predicted for different soil types using aerobic biodegradation rate constants estimated from the measured soil-gas data combined with conservative estimates of source concentrations. The modeling indicates that the vertical screening distance of 6 feet (1.8 m) recommended for dissolved-phase sources is applicable for 1,2-DCA below certain threshold concentrations in groundwater, while 15 feet (4.6 m) recommended for light nonaqueous phase liquid (LNAPL) sources is applicable for sites with clay and loam soils in the vadose zone, but not sand, if 1,2-DCA concentrations in groundwater exceed 150 μg/L. This dependence of the predicted vertical screening distances on soil type places added emphasis on proper soil characterization for VI screening at sites with 1,2-DCA sources. The soil-gas data suggests that a vertical screening distance of 15 feet (4.6 m) is necessary for both dissolved-phase and LNAPL sources.     

Field Study of Vertical Screening Distance Criteria for Vapor Intrusion of Ethylene Dibromide

Several regulatory agencies recommend screening petroleum vapor intrusion (PVI) sites based on vertical screening distance between a petroleum hydrocarbon source in soil or groundwater and a building foundation. U.S. Environmental Protection Agency (U.S. EPA) indicate the risk of PVI is minimal at buildings that are separated by more than 6 feet (1.8 m) from a dissolved-phase source and 15 feet (4.6 m) from a light nonaqueous phase liquid (LNAPL) source. This vertical screening distance method is not, however, recommended at sites with leaded gasoline sources containing ethylene dibromide (EDB) because of a lack of field data to document EDB attenuation in the vadose zone. To help address this gap, depth-discrete soil-gas samples were collected at a leaded gasoline release site in Sobieski, Minnesota (USA). The maximum concentration of EDB in groundwater (175 μg/L) at the site was high relative to those observed at other leaded gasoline release sites. Soil gas was analyzed for EDB using a modification of U.S. EPA Method TO-14A that achieved analytical detection limits below the U.S. EPA Vapor Intrusion Screening Level (VISL) for EDB based on a 10⁻⁶ cancer risk (<0.16 μg/m³). Concentrations of EDB in soil gas above LNAPL reached as high as 960 μg/m³ and decreased below the VISL within a source-separation distance of 7 feet. This result coupled with BioVapor model predictions of EDB concentrations indicate that vertical screening distances recommended by regulatory agencies at PVI sites are generally applicable for EDB over the range of anticipated source concentrations and soil types at most sites.     

Spatial Variability of Soil-Gas Concentrations near and beneath a Building Overlying Shallow Petroleum Hydrocarbon–Impacted Soils

Data requirements for assessing the significance of the soil vapor intrusion pathway are evolving, and the collection and interpretation of subslab and near-slab soil-gas samples are under discussion. The potential for different assessment paradigms for aerobically biodegradable and recalcitrant chemicals is also frequently debated. In this work, the soil-gas distribution beneath and around a slab-on-grade building overlying shallow (0.5 to >1.5 m below ground surface) petroleum hydrocarbon–impacted coarse alluvial soils was studied. The study spanned about 12 months, including the sampling of soil-gas hydrocarbon and oxygen concentrations, subslab soil vs. building pressure differentials and included weather conditions. Three-dimensional soil-gas concentration "snapshots" using samples from 79 soil-gas sampling points are presented here. Significant spatial variability was observed with hydrocarbon and oxygen concentrations ranging from about <0.01 to 200 mg/L and 0 to 21% v/v, respectively. The presence of oxygen and the depth to petroleum-impacted soils appeared to be the dominant factors in controlling the soil-gas distribution; the depletion of hydrocarbons over short lateral and vertical distances (<2 m) was observed in the well-oxygenated regions. Composition data suggest preferential biodegradation of lighter compounds at some points, as reflected in the ratio of the masses of chemicals eluting on the gas chromatography between methane and pentane (C1 and C5) and all others after pentane (>C5).     

Evaluation of Seasonal Factors on Petroleum Hydrocarbon Vapor Biodegradation and Intrusion Potential in a Cold Climate

A detailed seasonal study of soil vapor intrusion at a cold climate site with average yearly temperature of 1.9 °C was conducted at a house with a crawlspace that overlay a shallow dissolved‐phase petroleum hydrocarbon (gasoline) plume in North Battleford, Saskatchewan, Canada. This research was conducted primarily to assess if winter conditions, including snow/frost cover, and cold soil temperatures, influence aerobic biodegradation of petroleum vapors in soil and the potential for vapor intrusion. Continuous time‐series data for oxygen, pressure differentials, soil temperature, soil moisture, and weather conditions were collected from a high‐resolution monitoring network. Seasonal monitoring of groundwater, soil vapor, crawlspace air, and indoor air was also undertaken. Petroleum hydrocarbon vapor attenuation and biodegradation rates were not significantly reduced during low temperature winter months and there was no evidence for a significant capping effect of snow or frost cover that would limit oxygen ingress from the atmosphere. In the residual light nonaqueous phase liquid (LNAPL) source area adjacent to the house, evidence for biodegradation included rapid attenuation of hydrocarbon vapor concentrations over a vertical interval of approximately 0.9 m, and a corresponding decrease in oxygen to less than 1.5% v/v. In comparison, hydrocarbon vapor concentrations above the dissolved plume and below the house were much lower and decreased sharply within a few tens of centimeters above the groundwater source. Corresponding oxygen concentrations in soil gas were at least 10% v/v. A reactive transport model (MIN3P‐DUSTY) was initially calibrated to data from vertical profiles at the site to obtain biodegradation rates, and then used to simulate the observed soil vapor distribution. The calibrated model indicated that soil vapor transport was dominated by diffusion and aerobic biodegradation, and that crawlspace pressures and soil gas advection had little influence on soil vapor concentrations.     

NAPL source zone depletion model and its application to railroad-tank-car spills

We developed a new semi-analytical source zone depletion model (SZDM) for multicomponent light nonaqueous phase liquids (LNAPLs) and incorporated this into an existing screening model for estimating cleanup times for chemical spills from railroad tank cars that previously considered only single-component LNAPLs. Results from the SZDM compare favorably to those from a three-dimensional numerical model, and from another semi-analytical model that does not consider source zone depletion. The model was used to evaluate groundwater contamination and cleanup times for four complex mixtures of concern in the railroad industry. Among the petroleum hydrocarbon mixtures considered, the cleanup time of diesel fuel was much longer than E95, gasoline, and crude oil. This is mainly due to the high fraction of low solubility components in diesel fuel. The results demonstrate that the updated screening model with the newly developed SZDM is computationally efficient, and provides valuable comparisons of cleanup times that can be used in assessing the health and financial risk associated with chemical mixture spills from railroad-tank-car accidents.     

Evaluation of Vapor Intrusion Risk from Ethylene Dibromide Using the Vertical Screening Distance Approach

Vapor intrusion (VI) occurs when volatile contaminants in the subsurface migrate through the vadose zone into overlying buildings. The 2015 U.S. EPA petroleum VI guidance recommends that additional investigation of the VI risk from gasoline hydrocarbons at the underground storage tank (UST) sites is not necessary where the vertical distance between a building and a vapor source exceeds a recommended vertical screening distance. However, due to the lack of soil-gas data on the attenuation of ethylene dibromide (EDB), additional VI investigations to evaluate VI risk from EDB are recommended at UST sites with leaded gasoline releases containing EDB. We analyzed soil-gas and groundwater concentrations of EDB from eight petroleum UST sites using a new analytical method with soil-gas detection limit <0.16 μg/m³ EDB (VI screening level at the 10⁻⁶ risk level). The analysis included (1) assessing the frequency of EDB detections ≤0.16 μg/m³ at various vertical separation distances and (2) predicting vertical screening distances for EDB using the U.S. EPA PVIScreen model for different soil types in the vadose zone above dissolved-phase and LNAPL sources. Ranges of estimated aerobic biodegradation rate constants for EDB, air exchange rates for residential buildings, and source vapor concentrations for other constituents were combined with conservative estimates of EDB source concentrations as model inputs. Concentrations of EDB in soil-gas indicated that the U.S. EPA recommended vertical screening distances are protective of VI risk from EDB. Conversely, vertical screening distances predicted by modeling were >6 ft (1.8 m) for sites with sand and loam soil above dissolved phase sources and >15 ft (4.6 m) for sites with sand soil above LNAPL sources. This predicted dependence on the vapor source type and soil type in the vadose zone highlights the importance of soil characterization for VI screening at sites with EDB sources.     

Use of LIF for Real-Time In-Situ Mixed NAPL Source Zone Detection

The site characterization and analysis cone penetrometer system (SCAPS), equipped with realtime fluorophore detection capabilities, was used to delineate subsurface contaminant releases in an area where plating shop waste was temporarily stored. Records indicated that various nonaqueous phase liquids (NAPLs) were released at the site. The investigators advanced the SCAPS laser-induced fluorescence (LIF) sensor to depths beneath the water table of the principal water-bearing zone. The water table was located approximately 6 feet (1.8 m) below ground surface (bgs) across the site. Fluorescence, attributed to fuel compounds commingled with chlorinated solvents, was observed at depths ranging from 4.0 to 11.5 feet (1.2 to 3.5 m) bgs. Fluorescence, attributed to naturally occurring organic materials (by process of elimination and spectral characteristics) commingled with chlorinated solvent constituents, was observed at depths ranging from approximately 13 to 40 feet (4.0 to 12.2 m) bgs. Fluorescence responses from compounds confirmed to be commingled with chlorinated solvents indicates that the SCAPS fluorophore detection system is capable of indirectly delineating vadose zone and subaqueous chlorinated solvents and other dense nonaqueous phase liquids (DNAPLs) at contaminant release sites. This confirmation effort represents the first documented account of the successful application of LIF to identify a mixed DNAPL/LNAPL source zone.     

Vapor Intrusion Screening at Petroleum UST Sites

Detailed site investigations to assess potential inhalation exposure and risk to human health associated with the migration of petroleum hydrocarbon vapors from the subsurface to indoor air are frequently undertaken at leaking underground storage tank (UST) sites, yet documented occurrences of petroleum vapor intrusion are extremely rare. Additional assessments are largely driven by low screening‐level concentrations derived from vapor transport modeling that does not consider biodegradation. To address this issue, screening criteria were developed from soil‐gas measurements at hundreds of petroleum UST sites spanning a range of environmental conditions, geographic regions, and a 16‐year time period (1995 to 2011). The data were evaluated to define vertical separation (screening) distances from the source, beyond which, the potential for vapor intrusion can be considered negligible. The screening distances were derived explicitly from benzene data using specified soil‐gas screening levels of 30, 50, and 100 µg/m³ and nonparametric Kaplan‐Meier statistics. Results indicate that more than 95% of benzene concentrations in soil gas are ≤30 µg/m³ at any distance above a dissolved‐phase hydrocarbon source. Dissolved‐phase petroleum hydrocarbon sources are therefore unlikely to pose a risk for vapor intrusion unless groundwater (including capillary fringe) comes in contact with a building foundation. For light nonaqueous‐phase liquid (LNAPL) hydrocarbon sources, more than 95% of benzene concentrations in soil gas are ≤30 µg/m³ for vertical screening distances of 13 ft (4 m) or greater. The screening distances derived from this analysis are markedly different from 30 to 100 ft (10 to 30 m) vertical distances commonly found cited in regulatory guidance, even with specific allowances to account for uncertainty in the hydrocarbon source depth or location. Consideration of these screening distances in vapor intrusion guidance would help eliminate unnecessary site characterization at petroleum UST sites and allow more effective and sustainable use of limited resources.     

Transition probability/Markov chain analyses of DNAPL source zones and plumes

At sites where a dense nonaqueous phase liquid (DNAPL) was spilled or released into the subsurface, estimates of the mass of DNAPL contained in the subsurface from core or monitoring well data, either in the nonaqueous or aqueous phase, can be highly uncertain because of the erratic distribution of the DNAPL due to geologic heterogeneity. In this paper, a multiphase compositional model is applied to simulate, in detail, the DNAPL saturations and aqueous-phase plume migration in a highly characterized, heterogeneous glaciofluvial aquifer, the permeability and porosity data of which were collected by researchers at the University of Tübingen, Germany. The DNAPL saturation distribution and the aqueous-phase contaminant mole fractions are then reconstructed by sampling the data from the forward simulation results using two alternate approaches, each with different degrees of sampling conditioning. To reconstruct the DNAPL source zone architecture, the aqueous-phase plume configuration, and the contaminant mass in each phase, one method employs the novel transition probability/Markov chain approach (TP/MC), while the other involves a traditional variogram analysis of the sampled data followed by ordinary kriging. The TP/MC method is typically used for facies and/or hydraulic conductivity reconstruction, but here we explore the applicability of the TP/MC method for the reconstruction of DNAPL source zones and aqueous-phase plumes. The reconstructed geometry of the DNAPL source zone, the dissolved contaminant plume, and the estimated mass in each phase are compared using the two different geostatistical modeling approaches and for various degrees of data sampling from the results of the forward simulation. It is demonstrated that the TP/MC modeling technique is robust and accurate and is a preferable alternative compared to ordinary kriging for the reconstruction of DNAPL saturation patterns and dissolved-phase contaminant plumes.     

Empirical Assessment of Ground Water–to-Indoor Air Attenuation Factors for the CDOT-MTL Denver Site

The area surrounding the Colorado Department of Transportation Materials Testing Laboratory in Denver was the subject of intense investigation, involving the collection of thousands of ground water, soil-gas, and indoor air samples in order to investigate indoor air impacts associated with a subsurface release of chlorinated solvents. The preremediation portion of that data set is analyzed and reduced in this work to ground water–to-indoor air attenuation factors (α_gw= the ratio of the measured indoor air concentration to the soil-gas concentration predicted to be in equilibrium with the local ground water concentration). The empirical α_gw values for this site range from about 10⁻⁶ to 10⁻⁴ with an overall average of 3 × 10⁻⁵ (μg/L indoor air)/(μg/L soil gas). The analysis of this data set highlights the need for a thorough data review and data screening when using large data sets to derive empirical relationships between subsurface concentrations and indoor air. More specifically, it is necessary to identify those parts of the data that contain a strong vapor intrusion pathway signal, which generally will require concentrations well above reported detection levels combined with spatial or temporal correlation of subsurface and indoor concentrations.     

A Simple Model of Soil-Gas Concentrations Sparged into an Unlined Unsaturated Zone

We derive an analytical model of soil-gas contamination sparged into an imlined unsaturated zone. A nonaqueous phase liquid (NAPL) source lies in the capillary fringe, with an exponential sparge constant within the radius of influence and a constant ambient evaporation rate beyond. Advection, diffusion, and dispersion govern the conservative soil-gas response, expressed as a quasi-steady series solution with radial Bessel and hyperbolic vertical dependence. Simulations suggest that sparged contamination initially spreads beyond the radius of influence down a negative gradient. This gradient eventually reverses, leading to a subsequent influx of ambient contamination. Soil-gas concentrations accordingly reflect slowly varying source conditions as well as slowly varying diffusive transport through the radius of influence. The two time scales are independent: One depends on NAPL, airflow, and capillary fringe characteristics, the other on soil moisture, gaseous diffusivity, and unsaturated zone thickness. The influx of ambient contamination generates an asymptotic soil-gas concentration much less than the initial source concentration. The simple model is applied to a pilot-scale sparging study at Plattsburgh Air Force Base in upstate New York, with physically plausible results.     

Development and Testing of a Field Screening Method Based on Bubbling Extraction and Photoionization Detection for Measurement of Benzene and Total VOCs

A field screening method was developed for rapid measurement of benzene and gasoline range total petroleum hydrocarbons (TPHg) concentrations in groundwater. The method is based on collecting photoionization detector (PID) measurements from vapor samples. The vapor samples are collected by bubbling air through groundwater samples (air sparging) with a constant volume, temperature and sparging rate. The level of accuracy, sensitivity, precision, and statistical significance of the estimated concentrations, derived from the screening method, are comparable to conventional laboratory analytical results at concentrations equal to or greater than 150 µg/L for benzene and greater than 50 µg/L for TPHg. The method's concentration estimations can assist in making real‐time decisions regarding location of dissolved plumes and light nonaqueous phase liquid (LNAPL) source zones at many fuel release sites. The screening method was tested in the laboratory and in the field with 208 and 107 samples, respectively. The study concludes that the screening method can be used as a tool to aid in completing a site conceptual model as well as analyzing groundwater from monitoring wells.     

Measurement of Carbon Dioxide in Soil Gases for Indication of Subsurface Hydrocarbon Contamination

A preliminary field evaluation of a new application of soil-gas measurement for delineation of subsurface organic contamination is described. The method measures carbon dioxide concentrations in soil gases and is based on the hypothesis that carbon dioxide concentrations from subsurface oxidation of organic compounds will be porportional to the extent of organic contamination. A correlation coefficient (r) of 0.81 (n=6) was observed between ground water dissolved organic carbon ground water concentrations and carbon dioxide concentrations in the overlying soil gases at one site. Soil-gas carbon dioxide concentrations measured ranged from 0.09 percent to 0.45 percent.     

Evidence for Instantaneous Oxygen-Limited Biodegradation of Petroleum Hydrocarbon Vapors in the Subsurface

Petroleum hydrocarbon vapors biodegrade aerobically in the subsurface. Depth profiles of petroleum hydrocarbon vapor and oxygen concentrations from seven locations in sandy and clay soils across four states of Australia are summarized. The data are evaluated to support a simple model of biodegradation that can be used to assess hydrocarbon vapors migrating toward built environments. Multilevel samplers and probes that allow near‐continuous monitoring of oxygen and total volatile organic compounds (VOCs) were used to determine concentration depth profiles and changes over time. Collation of all data across all sites showed distinct separation of oxygen from hydrocarbon vapors, and that most oxygen and hydrocarbon concentration profiles were linear or near linear with depth. The low detection limit on the oxygen probe data and because it is an in situ measurement strengthened the case that little or no overlapping of oxygen and hydrocarbon vapor concentration profiles occurred, and that indeed oxygen and hydrocarbon vapors were largely only coincident near the location where they both decreased to zero. First‐order biodegradation rates determined from all depth profiles were generally lower than other published rates. With lower biodegradation rates, the overlapping of depth profiles might be expected, and yet such overlapping was not observed. A model of rapid (instantaneous) reaction of oxygen and hydrocarbon vapors compared to diffusive transport processes is shown to explain the important aspects of the 13 depth profiles. The model is simply based on the ratio of diffusion coefficients of oxygen and hydrocarbon vapors, the ratio of the maximum concentrations of oxygen and hydrocarbon vapors, the depth to the maximum hydrocarbon source concentration, and the stoichiometry coefficient. Whilst simple, the model offers the potential to incorporate aerobic biodegradation into an oxygen‐limited flux‐reduction approach for vapor intrusion assessments of petroleum hydrocarbon compounds.     

Subsurface Venting of Vapors Emanating from Hydrocarbon Product on Ground Water

The results of an API-sponsored pilot-scale subsurface venting system study are presented. The purpose of this study was to evaluate the effectiveness of forced venting techniques in controlling and removing hydrocarbon vapors from a subsurface formation. Both qualitative and quantitative sampling and analytical procedures were developed to measure hydrocarbon vapors extracted from the soil. Vapor recovery and equivalent liquid product recovery rates were measured at each test cell evacuation rate.
Two identical test cells were installed. Each cell contained 16 vapor monitoring probes spaced at distances from 4 to 44 feet from a vapor extraction (vacuum) well. Each cell was also configured with two air inlet wells to allow atmospheric air to enter the subsurface formation. The vapor monitoring probes were installed at three discrete elevations above the capillary zone. In situ vapor samples were obtained periodically from these probes to measure changes in vapor concentration and composition while extracting vapors from the vacuum well at three different flow rates (18.5 scfm, 22.5 scfm and 39.8 scfm). In situ vapor samples were analyzed using a portable gas chromatograph to quantify and speciate the vapors. Vacuum levels were also measured at each vapor sampling probe and at the vacuum well.
The soil venting techniques evaluated during this study offer an alternative approach for controlling and eliminating spilled or leaked hydrocarbons from sand or gravel formations of high porosity and moderate permeability. These techniques may also be used to augment conventional liquid recovery methods. The data collected during this study will be useful in optimizing subsurface venting systems for removing and controlling hydrocarbon vapors in soil. Study results indicate pulsed venting techniques may offer a cost-effective means of controlling or eliminating hydrocarbon vapors in soil.     

Analytical Solutions for Free-Hydrocarbon Recovery Using Skimmer and Dual-Pump wells

Accidental release of petroleum hydrocarbons to the subsurface may occur through spills around refineries, leaking pipelines, storage tanks, or other sources. If the spill is large, the hydrocarbon liquids may eventually reach a water table and spread laterally in a pancake-like lens. Hydrocarbons that exist as a separate phase are termed light nonaqueous phase liquids (LNAPLs). The portion of the LNAPL that is mobile, not entrapped as residual saturation, is termed "free product."
This paper presents new analytical solutions for the design of long-term free-product recovery from aquifers with skimmer, single- and dual-pump wells. The solutions are for steady-state flow, based on the assumption of vertical equilibrium, and include the effect of coning of LNAPL, air, and water on flow. The solutions are valid for soils of large hydraulic conductivity where the effect of capillary pressure on coning is small.
The results show how to estimate the maximum rate of inflow of LNAPL for skimmer wells, i.e., wells in which LNAPL is recovered with little or no water production. The paper also shows how to calculate the increase in LNAPL recovery when water is pumped by single- or dual-pump wells. A simple equation is given that can be used to adjust the water rate to avoid smearing of the LNAPL below the water table.     

Geochemical effects on metals following permanganate oxidation of DNAPLs

The application of in situ chemical oxidation for dense, nonaqueous phase liquid (DNAPL) remediation requires delivery of substantial levels of oxidant chemicals into the subsurface to degrade target DNAPLs and to satisfy natural oxidant demand. This practice can raise questions regarding changes in subsurface conditions, yet information regarding potential effects, especially at the field scale, has been lacking. This paper describes an evaluation of the effects on metals associated with in situ chemical oxidation using potassium permanganate at Launch Complex 34 (LC34), Cape Canaveral Air Station, Florida. At LC34, high concentrations of permanganate (1 to 2 wt%) were injected into the subsurface as part of a demonstration of DNAPL remediation technologies. In a companion experimental effort at the Colorado School of Mines, field samples were characterized and laboratory batch and mini-column studies were completed to assess effects of permanganate oxidation on metals in the subsurface one year after completion of the field demonstration. Results indicated there was potential for long-term immobilization of a portion of introduced manganese and no treatment-induced loss in subsurface permeability due to deposition of manganese oxides particles, which are a product of the oxidation reactions. Permanganate treatment did cause elevated manganese, chromium, and nickel concentrations in site ground water within the treated region. Some of these metals effects can be attenuated during downgradient flow through uncontaminated and untreated aquifer sediments.     

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.