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.     

Simulation of Vapor Transport Through the Unsaturated Zone — Interpretation of Soil-Gas Surveys

Soil-gas surveys are becoming more widely accepted as a tool for the preliminary determination of the extent of soil and ground water contamination by volatile organic compounds (VOCs). The interpretation of the results of published soil-gas surveys has been necessarily limited and qualitative due to a lack of adequate models. There has been considerable effort in the recent past to characterize the transport and fate of pesticides in soil. However, the behavior of pesticides generally differ substantially from those of VOCs.
This paper presents a computer model developed to simulate the diffusive transport of VOC vapor through unsaturated soils using a two-dimensional, finite-difference, solution to Fick's second law of diffusion. An effective diffusion coefficient that incorporates the effects of tortuosity, moisture content, and soil organic carbon content is computed. Although the model has not been validated due to the unavailability of adequate field or laboratory data, nevertheless, sensitivity analyses demonstrate the importance of soil moisture and, secondarily, organic matter content in controlling the migration of VOC vapor through the unsaturated zone. The interpretation of soil-gas surveys can be complicated by unknown spatial heterogeneities in soil moisture and organic carbon content, temporal variations in moisture content, extent of contaminant migration as a non-aqueous phase liquid and by the unknown extent of VOC liquid and contaminated ground water.     

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).     

Relationship between soil cellulose decomposition and oil contamination after an oil spill at Swanson Creek, Maryland

In wetlands, oil spills may affect decomposition in soils, which controls organic matter accumulation, the primary contributor to positive elevation change. In this study we examined how oil from a spill affected organic matter decomposition in soils of a brackish intertidal marsh in Maryland. Decomposition was measured using the cellulose (cotton) strip technique. Cellulose decomposition was not affected by concentrations of different oil components (total hydrocarbons, total resolved hydrocarbons, and polycyclic aromatic hydrocarbons). Rather, other abiotic characteristics of the soil had strong effects on decomposition rates, including strong negative effects of soil depth and salinity, and a positive effect of pH. Measures of soil fertility (NH(4)-N and PO(4)-P) were not significantly related to cellulose decomposition. Thus, we conclude that decomposition was controlled more by naturally occurring environmental factors rather than by exposure to oil.     

Ground Water Remediation Using an Extraction, Treatment, and Recharge System

Ground water remediation of volatile organic compound (VOC) contamination at a site in Michigan was initiated as a result of a consent agreement between the Michigan Department of Natural Resources (MDNR) and the responsible party. Under the direction of the MDNR, the responsible party conducted a remedial investigation/feasibility study using federal guidelines to define the extent of contamination at the site and to select a response action for site remediation. The selected alternative included a combination of ground water extraction, treatment, and recharge, and soil flushing. The extraction system withdraws ground water from various depths in heavily contaminated areas. The ground water is treated using an air stripper. A spray distribution system spreads effluent from the stripper over a recharge basin constructed over the most contaminated areas. Additional contaminant removal is achieved by volatilization from the spray and percolation through the gravel bed. Recharge water moves downward through the contaminated soils, thus flushing residual soil contaminants. The initial operating data demonstrated that the system can effectively remove trichloroethylene (TCE) from ground water (approximately 95 percent overall removal efficiency). The annualized capital and operation and maintenance (O & M) costs of the remedial action were estimated for several operating periods (15, 20, and 30 years).     

Comparison of Two Integrated Methods for the Collection and Analysis of Volatile Organic Compounds in Ground Water

The principal difficulties with determinations of volatile organic compounds (VOCs) in ground water are the reliability of sampling procedures and analytical methods. Two integrated methods have been developed for routine sampling, processing, and analysis of VOCs in ground water. These methods involve in situ collection of ground water using a modified syringe sampler from PVC piezometers or using dedicated glass syringes from stainless steel multilevel bores. The samples are processed in the syringe using purge and trap or microsolvent extraction and analyzed by GC/MSD.
The modified purge-and-trap method is time-consuming and limited to volatile organic compounds. However, it is extremely sensitive and flexible: the volume of sample used can be varied by the use of different-size glass syringes (sample volumes from 1 to 100 mL).
In cases where extremely low sensitivity (<10 mg 1⁻¹) is not critical, the microextraction technique is a more cost-effective method, allowing twice as many samples to be analyzed in the same time as the purge-and-trap method. It enables less volatile compounds such as polynuclear aromatic hydrocarbons, phenol, and cresols to be analyzed in the same GC run. Also, the microextraction method can be used in the field to avoid delays associated with transportation of ground water samples to the laboratory.     

Ground Water Contamination in Kuwait Resulting from the 1991 Gulf War: A Preliminary Assessment

A large number of oil wells in Kuwait were damaged and ignited by the retreating Iraqi troops during the 1991 Gulf War. The resulting spillage of huge volumes of crude oil on the surface gave rise to oil lakes and crude oil–impregnated soil. Moreover, products of crude oil combustion had spread over a large tract of the ground surface, causing widespread contamination of soil. Hydrocarbon contamination of ground water by the infiltrating runoff water carrying the contaminants from the surface soil to the water table and/or through direct contact with the crude oil leaking through the damaged casing in the subsurface was feared. This preliminary study was carried out to investigate the extent and nature of this possible contamination of ground water. The results indicate that the shallow fresh water lenses present under the Umm Al-Aish water field and in the southeastern parts of the Raudhatain water field in North Kuwait were affected by hydrocarbon pollution. Standard methods like the determination of the contents of the total petroleum hydrocarbon by the Fourier transform infrared method and 16 polyaromatic hydrocarbons using the gas chromatography-mass spectrometry method did not work well, possibly due to the environmental degradation of the crude oil over time. The fluorescence methods and the total organic carbon and total organic matter gave better indications of the intensity and the extent of ground water pollution. The brackish water fields of South and Central Kuwait were, however, free of any indications of hydrocarbon contamination.     

Field Trapping of Subsurface Vapor Phase Petroleum Hydrocarbons

Soil gas samples from intact soil cores were collected on adsorbents at a field site, then thermally desorbed and analyzed by laboratory gas chromatography (GC). Vertical concentration profiles of predominant vapor phase petroleum hydrocarbons under ambient conditions were obtained for the zone directly above the capillary fringe. Water and residual phase weathered aviation gasoline were present in this region of the profile.
The sampling, trapping, and GC methodology was effective in most respects. Reproducibility, trapping, and desorption efficiency were generally satisfactory, and different sorbent tubes gave similar results. A minor shortcoming of the method occurred with the most volatile compound, 2,3-dimcthylbutane, which was poorly retained during several weeks of storage lime and was also poorly desorbed.
Vapor phase concentrations of predominant hydrocarbon compounds all increased with depth at one sampling location. At a more highly contaminated location, concentrations of highly volatile compounds increased with depth while concentrations of less volatile compounds remained constant or decreased, possibly indicating distillation effects. Scatier in the data was attributed to heterogeneities in water and residual phase distribution.     

Predicting Soil-Water and Soil-Air Transport Properties and Their Effects on Soil-Vapor Extraction Efficiency

Accurate prediction of water and air Iran sport parameters in variably saturated soil is necessary for modeling of soil-vapor extraction (SVE) at soil sites contaminated with volatile organic chemicals (VOCs). An expression for predicting saturated water permeability (k_l,s) in undisturbed soils from the soil total porosity and the field capacity soil-water content was developed by fitting a tortuous-tube fluid flow model to measured water permeability and gas diffusivity data. The new k_l,s expression gave accurate predictions when tested against independent k_l,s data. The k_l,s expression was implemented in the Campbell relative water permeability model to yield a predictive model for water permeability in variably saturated, undisturbed soil. The water permeability model, together with recently developed predictive equations for gas permeability and gas diffusivity, was used in a two-dimensional numerical SVE model that also included non-equilibrium mass transfer of VOC from a separate phase (nonaqueous phase liquid [NAPL]) to the air phase. SVE: calculations showed that gas permeability is likely the most important factor controlling VOC migration and vapor extraction efficiency. Water permeability and gas diffusivity effects became significant at water contents near and above field capacity. The NAPL-air mass transfer coefficient also had large impacts on simulated vapor extraction efficiency. The calculations suggest that realistic SVE models need to include predictive expressions for both conveciive, diffusive. and phase-partitioning processes in natural, undisturbed soils.     

An Overview of In Situ Air Sparging

In situ air sparging (IAS) is becoming a widely used technology for remediating sites contaminated by volatile organic materials such as petroleum hydrocarbons. Published data indicate that the injection of air into subsurface water saturated areas coupled with soil vapor extraction (SVE) can increase removal rates in comparison to SVE alone for cases where hydrocarbons are distributed within the water saturated zone. However, the technology is still in its infancy and has not been subject to adequate research, nor have adequate monitoring methods been employed or even developed. Consequently, most IAS applications are designed, operated, and monitored based upon the experience of the individual practitioner.
The use of in situ air sparging poses risks not generally associated with most practiced remedial technologies: air injection can enhance the undesirable off-site migration of vapors and ground water contamination plumes. Migration of previously immobile liquid hydrocarbons can also be induced. Thus, there is an added incentive to fully understand this technology prior to application.
This overview of the current state of the practice of air sparging is a review of available published literature, consultation with practitioners, a range of unpublished data reports, as well as theoretical considerations. Potential strengths and weaknesses of the technology are discussed and recommendations for future investigations are given.     

Remediation of the Wells G & H Superfund Site,Woburn, Massachusetts

Remediation of ground water and soil contamination at the Wells G & H Superfund Site, Woburn, Massachusetts, uses technologies that reflect differences in hydrogeologic settings, concentrations of volatile organic compounds (VOCs), and costs of treatment. The poorly permeable glacial materials that overlie fractured bedrock at the W.R. Grace property necessitate use of closely spaced recovery wells. Contaminated ground water is treated with hydrogen peroxide and ultraviolet (UV) oxidation. At UniFirst, a deep well completed in fractured bedrock removes contaminated ground water, which is treated by hydrogen peroxide, UV oxidation, and granular activated carbon (GAC). The remediation system at Wildwood integrates air sparging, soil-vapor extraction, and ground water pumping. Air stripping and GAC are used to treat contaminated water; GAC is used to treat contaminated air. New England Plastics (NEP) uses air sparging and soil-vapor extraction to remove VOCs from the unsaturated zone and shallow ground water. Contaminated air and water are treated using separate GAC systems. After nine years of operation at W.R. Grace and UniFirst, 30 and 786 kg, respectively, of VOCs have been removed. In three years of operation, 866 kg of VOCs have been removed at Wildwood. In 15 months of operation, 36 kg of VOCs were removed at NEP. Characterization work continues at the Olympia Nominee Trust, Whitney Barrel, Murphy Waste Oil, and Aberjona Auto Parts properties. Risk assessments are being finalized that address heavy metals in the floodplain sediments along the Aberjona River that are mobilized from the Industri-Plex Superfund Site located a few miles upstream.     

Differentiation of the Origins of BTX in Ground Water Using Multivariate Plots

Multivariate plots were utilized to create fingerprints of aromatic hydrocarbon residues in ground water. The technique allows hydrogeologists to distinguish between residues of benzene, toluene, ethyl benzene, and total xylenes originating from ground water contact with petroleum in natural deposits and refined petroleum waste products. Examples were taken from deep-well injection of refinery wastes, natural petroleum deposits, municipal and industrial landfill leachates, coal tar and creosote contaminated waters, and varnish industry contaminated ground water. The data were plotted from ASCII files generated through either Lotus 123™ or a database (The Manager™) report program, using a simple Fortran interactive program with Plot88™ subroutines.     

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.     

An Evaluation of Some Systems for Sampling Gas-Charged Ground Water for Volatile Organic Analysis

Loss of volatile organics during sampling is a well-recognized source of bias in ground water monitoring; sampling protocols attempt to minimize such loss. Such bias could be enhanced for ground water highly charged with dissolved gases such as methane. Such ground water was the object of this study. A positive-displacement bladder pump, a momentum-lift pump and a suction-lift, peristaltic pump were employed in sampling both methane-charged ground water for volatile aromatic hydrocarbons and a CO₂-charged reservoir water for volatile chlorinated hydrocarbons. In both cases, the suction-lift pump produced samples with a significant negative bias (9 to 33 percent) relative to the other methods. Little difference between samples produced by the other pump Systems was noted at the field site, but in sampling the reservoir, the bladder pump produced samples that were 13 to 19 percent lower in halocarbon concentration than were samples from the momentum-lift pump.
These negative biases are tentatively interpreted as losses due to volatilization during sampling. Slightly greater negative biases occur for compounds of higher volatility as estimated from their Henry's law constants. Additional studies appear to be warranted in order to adequately establish the scientific basis for recommending protocols for sampling ground water in which degassing could enhance the loss of volatile organics during sampling.     

Laboratory Comparison of Polyethylene and Dialysis Membrane Diffusion Samplers

The ability of diffusion samplers constructed from regenerated cellulose dialysis membrane and low density, lay flat polyethylene tubing to collect volatile organic compounds and inorganic ions was compared in a laboratory study. Concentrations of vinyl chloride, cis -1, 2-dichloroethene, bromochloromethane, trichloroethene, bromodichloromethane, and tetrachloroethene collected by both types of diffusion samplers reached equilibrium with the concentrations of these compounds in test solution within three days. Concentrations of bromide and iron collected by the dialysis membrane diffusion samplers reached equilibrium with the concentrations of these compounds in a test solution within three to seven days. No detectable concentrations of bromide or iron were found in polyethylene diffusion samplers even after 21 days. No measurable concentrations of aluminum, arsenic, barium, cadmium, chromium, iron, mercury, manganese, nickel, and lead, or sulfide, were leached out of dialysis membrane samplers over seven days. Compared with using a gas-tight syringe to sample the diffusion sampler, clipping the bag and pouring the water sample into a sample vial resulted in only a small 6.2% average loss of volatile organic compounds. Dialysis membrane diffusion samplers offer promise for use in sampling ground water for inorganic constituents as well as volatile organic compounds.     

Effects of land use on ground water quality in the Anoka Sand Plain Aquifer of Minnesota

We began a study, in 1996, to compare ground water quality under irrigated and nonirrigated agriculture, sewered and nonsewered residential developments, industrial, and nondeveloped land uses. Twenty-three monitoring wells were completed in the upper meter of an unconfined sand aquifer. Between 1997 and 2000, sampling occurred quarterly for major ions, trace inorganic chemicals, volatile organic compounds (VOCs), herbicides, and herbicide degradates. On single occasions, we collected samples for polynuclear aromatic hydrocarbons (PAHs), perchlorate, and coliform bacteria. We observed significant differences in water chemistry beneath different land uses. Concentrations of several trace inorganic chemicals were greatest under sewered urban areas. VOC detection frequencies were 100% in commercial areas, 52% in sewered residential areas, and <10% for other land uses. Median nitrate concentrations were greatest under irrigated agriculture (15,350 microg/L) and nonsewered residential areas (6080 microg/L). Herbicides and degradates of acetanilide and triazine herbicides were detected in 86% of samples from irrigated agricultural areas, 68% of samples from nonirrigated areas, and <10% of samples from other land uses. Degradates accounted for 96% of the reported herbicide mass. We did not observe seasonal differences in water chemistry, but observed trends in water chemistry when land use changes occurred. Our results show land use is the dominant factor affecting shallow ground water quality. Trend monitoring programs should focus on areas where land use is changing, while resource managers and planners must consider potential impacts of land use changes on ground water quality.     

Subsurface Transport of Inorganic and Organic Solutes from Experimental Road Spreading of Oil-Field Brine

A study designed to evaluate ground water quality changes resulting from spreading oil-field brine on roads for ice and dust control was conducted using a gravel roadbed that received weekly applications of brine eight times during the winter phase and 11 times during the summer phase of the study. A network of 11 monitoring wells and five pressure-vacuum lysimeters was installed to obtain ground water and soil water samples. Thirteen sets of water- quality samples were collected and analyzed for major ions, trace metals, and volatile organic compounds. Two sets of samples were taken prior to brine spreading, four sets during winter-phase spreading, five sets during summer- phase spreading, and two sets during the interim between the winter and summer phases. A brine plume delineated by elevated specific-conductance values and elevated chloride concentrations developed downgradient of the roadbed during both the winter and summer phases. The brine plume caused chloride concentrations in ground water samples to exceed U.S. EPA public drinking-water standards by two-fold during the winter phase and five-fold during the summer phase. No other major ions, trace metals, or volatile organic compounds exceeded the standards during the winter or summer phases. More than 99 percent dilution of the solutes in the brine occurred between the roadbed surface and the local ground water flow system. Further attenuation of calcium, sodium, potassium, and strontium resulted from adsorption, whereas further attenuation of benzene resulted from volatilization and adsorption.     

An Improved Gas Chromatographic Method for the Determination of C6–C12 Petroleum Hydrocarbons in Soil Water

In this work, investigations dealing with the determination of hydrocarbons in contaminated soil water are presented. The hydrocarbons under investigation range from low to high volatility compounds. A GC‐FID method was developed that due to its efficiency, routine suitability, relative rapidity, and low cost is suitable for the analysis of complex chemical mixtures of highly volatile hydrocarbons (with boiling points between 69 and 190°C). The standard used was a gasoline mixture with boiling points ranging from 100 to 190°C. For this standard, no supplementary preparation is needed and it is suitable for the whole range of hydrocarbons under investigation. The determination of the hydrocarbon content of the samples was performed applying univariate and multivariate statistical analysis to the experimental data. In the characterization of a contamination with highly volatile hydrocarbons of soil water originating from different depth layers from the chemistry location Leuna (Sachsen‐Anhalt, Germany), the advantages of a multivariate method are demonstrated in exemplary manner.     

Screening of Ground Water Samples for Volatile Organic Compounds Using a Portable Gas Chromatograph

A portable gas chromatograph was used to screen 32 ground water samples for volatile organic compounds. Seven screened samples were positive; four of the seven samples had volatile organic substances identified by second-column confirmation. Four of the seven positive, screened samples also tested positive in laboratory analyses of duplicate samples. No volatile organic compounds were detected in laboratory analyses of samples that headspace screening indicated to be negative. Samples that contained volatile organic compounds, as identified by laboratory analysis, and that contained a volatile organic compound present in a standard of selected compounds were correctly identified by using the portable gas chromatograph. Comparisons of screened-sample data with laboratory data indicate the ability to detect selected volatile organic compounds at concentrations of about 1 microgram per liter in the headspace of water samples by use of a portable gas chromatograph.     

Investigations at Sites Contaminated with Dense, Non-Aqueous Phase Liquids (NAPLs)

Increasingly, ground water supplies are being found to be contaminated with organic substances. Depending on the nature of these substances and the method by which they were introduced into the environment, they may form a second, dense liquid phase. Several such cases have been reported in the recent literature. In other cases, such a second phase might have actually been present but was not found because the principles governing its distribution were not understood and no effort was made to look for it. In this case, the undetected material could continue to migrate and act as a source of dissolved organics.
This article reviews the general principles governing the behavior of dense, immiscible second-phase organic liquids in both the unsaturated and saturated zones, based primarily on the petroleum industry literature for primary hydrocarbon migration and on the oil spill literature. This specialized knowledge can be used to conduct a meaningful and efficient investigation of such contamination sites and can also be used to select and implement successful remedial measures. Several actual case studies applying the principles of multi-phase flow are also presented.