Application of VLEACH to Vadose Zone Transport of VOCs at an Arizona Superfund Site

Cleanup standards for volatile organic compounds in thick vadose zones can be based on indirect risk (transport to ground water) when contamination is below depths of significant direct risk. At one Arizona Superfund site, a one-dimensional vadose zone transport model (VLE-ACH) was used to estimate the continued transport of VOCs from the vadose zone to ground water. VLEACH is a relatively simple and readily available model that proved useful for estimating indirect risk from VOCs in the vadose zone at this site. The estimates of total soil concentrations used as initial conditions for VLF.ACH incorporated a variety of data from the site. Soil gas concentrations were found to be more useful than soil matrix data for estimating total soil concentrations at this arid-zone site. A simple mixing cell model was used with the VLEACH-derived mass loading estimates from the vadose zone over time to estimate the resulting changes in ground water concentrations. For this site, the results of the linked VLEACH/mixing cell simulations indicate it is likely that the federal MCI. for TCE will be exceeded in underlying ground water if remedial action on I he vadose zone is not pursued.     

Factors Requiring Resolution in Installing Vadose Zone Monitoring Systems

Increasingly, regulations by federal, state and local agencies are being developed that require the installation of vadose zone monitoring systems for hazardous chemical facilities in addition to, or in lieu of, conventional ground water monitoring wells. Compared to a ground water monitoring approach, vadose zone monitoring systems may permit earlier detection of chemical leakage and less costly cleanup of contamination. The effective use of vadose zone monitoring systems in detecting contamination depends on many factors. Without proper consideration of these factors, a vadose zone monitoring system may not give as high a level of reliability as a ground water monitoring system.
Major factors to consider in installing a vadose zone monitoring system are: type of instrument to use, number of instruments, depth and location of instruments, and frequency of monitoring. Means to evaluate these factors in a comprehensive fashion have been lacking. Based on recent experience in installing and operating vadose zone monitoring systems, criteria and methods useful in resolving the preceding factors have been developed. Types of instruments can be classified as either direct (lysimeter, vapor probe) or indirect (tensiometer, conductivity probe). A combination of the two is needed for reliability. The depth, location and number of instruments depend on the geometry of the facility, the number and size of likely contaminant leakage points in engineered barriers, properties of the material being monitored, the effective radius of monitoring for each instrument, vadose zone properties, and types of remedial actions that are available. The freqency of monitoring largely depends on the rate of movement of the contaminant. Evaluating the preceding factors requires some level of modeling and preliminary field testing.     

Design, Installation, and Uses of Combination Ground Water and Gas Sampling Wells

Waste disposal sites with volatile organic compounds (VOCs) frequently contain contaminants that are present in both the ground water and vadose zone. Vertical sampling is useful where transport of VOCs in the vadose zone may effect ground water and where steep vertical gradients in chemical concentrations are anticipated. Designs for combination ground water and gas sampling wells place the tubing inside the casing with the sample port penetrating the casing for sampling. This physically interferes with pump or sampler placement. This paper describes a well design that combines a ground water well with gas sampling ports by attaching the gas sampling tubing and ports to the exterior of the casing. Placement of the tubing on the exterior of the casing allows exact definition of gas port depth, reduces physical interference between the various monitoring equipment, and allows simultaneous remediation and monitoring in a single well. The usefulness and versatility of this design was demonstrated at the Idaho National Engineering and Environmental Laboratory (INEEL) with the installation of seven wells with 53 gas ports, in a geologic formation consisting of deep basalt with sedimentary interbeds at depths from 7.2 to 178 m below land surface. The INEEL combination well design is easy to construct, install, and operate.     

Estimating Persistent Mass Flux of Volatile Contaminants from the Vadose Zone to Ground Water

Contaminants may persist for long time periods within low permeability portions of the vadose zone where they cannot be effectively treated and are a potential continuing source of contamination to ground water. Setting appropriate vadose zone remediation goals typically requires evaluating these persistent sources in terms of their impact on meeting ground water remediation goals. Estimating the impact on ground water can be challenging at sites with low aqueous recharge rates where vapor-phase movement is the dominant transport process in the vadose zone. Existing one-dimensional approaches for simulating transport of volatile contaminants in the vadose zone are considered and compared to a new flux-continuity-based assessment of vapor-phase contaminant movement from the vadose zone to the ground water. The flux-continuity-based assessment demonstrates that the ability of the ground water to move contaminant away from the water table controls the vapor-phase mass flux from the vadose zone across the water table. Limitations of these approaches are then discussed with respect to the required assumptions and the need to incorporate three-dimensional processes when evaluating vapor-phase transport from the vadose zone to the ground water. The carbon tetrachloride plume at the U.S. Department of Energy Hanford Site is used as the example site where persistent vadose zone contamination needs to be considered in the context of ground water remediation.     

EPA's Approach to Vadose Zone Monitoring at RCRA Facilities

The U.S. Environmental Protection Agency (EPA) recently proposed to amend federal regulations to require vadose zone monitoring at certain hazardous waste facilities. To support this proposal, EPA evaluated previous policy on vadose zone monitoring and examined advances in vadose zone monitoring technology. Changes in EPA vadose zone monitoring policy were driven by demonstrated advances in the available monitoring technology and improvements in understanding of vadose zone processes/When used under the appropriate conditions, currently available direct and indirect monitoring methods can effectively detect contamination that may leak from hazardous waste facilities into the vadose zone. Direct techniques examined include soil-core monitoring and soil-pore liquid monitoring. Indirect techniques examined include soil-gas monitoring, neutron moderation, complex resistivity, ground-penetrating radar, and electrical resistivity. Properly designed vadose zone monitoring networks can act as a complement to saturated zone monitoring networks at numerous hazardous waste facilities. At certain facilities, particularly those in arid climates where the saturated zone is relatively deep, effective vadose zone monitoring may allow a reduction in the scope of saturated zone monitoring programs.     

Design of Lysimeter Leak Detector Networks for Surface Impoundments and Landfills

Sampling of soil pore moisture in the vadose zone underneath land disposal facilities (landfills and surface impoundments) for hazardous waste has been suggested as an "early warning system" to detect leakage from these facilities. Some states require vadose zone moisture sampling at such sites. Given a leak of a particular size, mathematical models can estimate the necessary moisture sample volume collection times and lysimeter spacings to guarantee detection of the leak in a homogeneous medium. Examination of 47 hazardous waste sites existing in 1984 indicated the most were located in areas with water tables too shallow to permit vadose zone detection monitoring. Several of the 47 sites had soils that could be described as loamy sand, silt loam or silty clay. Using these three soils as examples, the process of lysimeter leak-detector network design has been illustrated. For a particular loamy sand with a saturates hydraulic conductivity of 10^-6 cm/ sec, the maximum ceramic lysimeter spacing is 15.5 feet at a depth of 30 feet to collec a moisture sample of 10 mL in one week from a 1 ft2 leak. For a silt loam, maximum lysimeter spacing would be 17 feet at depth of 15 feet. For silty clays, the maximum lysimeter spacing is 7 feet at a depth of 2 feet; maximum emplacement depth is about 9 feet. Calculations show that in some soils, suction lysimeters will not be able to collect usable moisture samples. Since soil properties vary widely and lysimeter spacing is strongly dependent on soil-moisture characteristics appropriate soil measurements and modeling must be performed at each disposal facility to estimate lysimete performance and to select locations for emplacement.     

Vadose Zone Monitoring: Experiences and Trends in the United States

The vadose zone is the portion of the geologic profile above a perennial aquifer. Inclusion of mandatory vadose zone monitoring techniques as an approach to aquifer protect ion was first proposed under the Resource Conservation and Recovery Act in the United States in 1978 and has since received increasing acceptance at federal and stale levels. The goals of a vadose zone characterization and monitoring effort are to establish background conditions, identify contaminant transport pathways, identify the extent and degree of existing contamination, establish the basis for monitoring network design, measure the parameters needed in a risk assessment, and provide detection of contaminant migration toward ground water resources. The benefits of vadose zone monitoring include early warning of contaminant migration, potential reduction of ground water monitoring efforts, reduction of contaminant spreading and volume, and reduced time and cost of remediation once a contaminant release occurs. Vadose zone characterization and monitoring techniques should be considered as critical hydrologic tools in the prevention of ground water resource degradation.     

Three-Dimensional Simulation of Volatile Organic Compound Mass Flux from the Vadose Zone to Groundwater

Low-permeability layers of the vadose zone containing volatile organic compounds (VOCs) may persist as source zones for long time periods and may provide contamination to groundwater. At sites with low recharge rates, where vapor migration is the dominant transport process, the impact of vadose zone sources on groundwater may be difficult to assess. Typical assessment methods include one-dimensional numerical and analytical techniques. The one-dimensional approaches only consider groundwater coupling options through boundary conditions at the water table and may yield artificially high mass flux results when transport is assumed to occur by gas-phase diffusion between a source and an interface with a zero concentration boundary condition. Improvements in mass flux assessments for VOCs originating from vadose zone sources may be obtained by coupling vadose zone gas transport and dissolved contaminant transport in the saturated zone and by incorporating the inherent three-dimensional nature of gas-phase transport, including the potential of density-driven advection. This paper describes a series of three-dimensional simulations using data from the U.S. Department of Energy's Hanford site, where carbon tetrachloride is present in a low-permeability zone about 30 m above the groundwater. Results show that, for most cases, only a relatively small amount of the contaminant emanating from the source zone partitions into the groundwater and that density-driven advection is only important when relatively high source concentrations are considered.     

Atrazine retention and degradation in the vadose zone at a till plain site in central Indiana

The vadose zone was examined as an environmental compartment where significant quantities of atrazine and its degradation compounds may be stored and transformed. The vadose zone was targeted because regional studies in the White River Basin indicated a large discrepancy between the mass of atrazine applied to fields and the amount of the pesticide and its degradation compounds that are measured in ground and surface water. A study site was established in a rotationally cropped field in the till plain of central Indiana. Data were gathered during the 1994 growing season to characterize the site hydrogeology and the distribution of atrazine, desethylatrazine, deisopropylatrazine, didealkylatrazine and hydroxyatrazine in runoff, pore water, and ground water. The data indicated that atrazine and its degradation compounds were transported from land surface to a depth of 1.5 m within 60 days of application, but were undetected in the saturated zone at nearby monitoring wells. A numerical model was developed, based on the field data, to provide information about processes that could retain and degrade atrazine in the vadose zone. Simulations indicated that evapotranspiration is responsible for surface directed soil-moisture flow during much of the growing season. This process causes retention and degradation of atrazine in the vadose zone. Increased residence time in the vadose zone leads to nearly complete transformation of atrazine and its degradation products to unquantified degradation compounds. As a result of macropore flow, small quantities of atrazine and its degradation compounds may reach the saturated zone.     

Vertical Contaminant Profiling of Volatile Organic* in a Deep Fractured Basalt Aquifer

Volatile organic compounds delected in ground water from wells at Test Area North (TAN) at the Idaho National Engineering Laboratory (INEL) prompted RCRA facility investigations in 1989 and 1990 and a CERCLA-driven RI/FS in 1992. In order to address ground water treatment feasibility, one of the main objectives, of the 1992 remedial investigation was to determine the vertical extent of ground water contamination, where the principle contaminant, of concern is trichloroethylene (TCE). It was hypothesized that a sedimentary interbed at depth in the fractured basalt aquifer could be inhibiting vertical migration of contaminants to lower aquifers. Due to the high cost of drilling and installation of ground water monitoring wells at this facility (greater than $100,000 per well), a real time method was proposed for obtaining and analyzing ground water samples during drilling to allow accurate placement of well screens in zones of predicted VOC contamination. This method utilized an inflatable pump packer pressure transducer system interfaced with a datalogger and PC at land surface. This arrangement allowed for real lime monitoring of hydraulic head above and below the packer to detect leakage around the packer during pumping and enabled collection of head data during pumping for estimating hydrologic properties. Analytical results were obtained in about an hour from an on-site mobile laboratory equipped with a gas chromalograplvmass spectrometer (GC/MS). With the hydrologic and analytical results in hand, a decision was made to either complete the well or continue drilling to the next test zone. In almost every case, analytical results of ground water samples taken from the newly installed wells closely replicated the water quality of ground water samples obtained through the pump packer system.     

A Comparison of Ground Water Monitoring Data from CERCLA and RCRA Sites

Ground water quality data generated during the investigation of 334 hazardous waste disposal sites were used to contrast the Resource Conservation and Recovery Act (RCRA) and Comprehensive Emergency Response, Compensation and Liability Act (CERCLA) monitoring. programs. The minimum RCRA-required network of four wells was equaled or exceeded at 94 percent of the 156 RCRA sites and 70 percent of the 178 CERCLA sites in the data base. A sampling frequency of four events per year or more was used at 60 percent of the RCRA sites compared to only 24 percent at the CERCLA sites. CERCLA records compiled to date indicate that 480 compounds have been detected and another 220 compounds have been tentatively identified in ground water in the vicinity of hazardous waste disposal sites. However, the composite data from 123 RCRA site monitoring programs only indicates the presence of 100 chemical substances. The most significant discrepancy in the RCRA detection monitoring program is that it only generates data on three of the 20 organic contaminants that have been most frequently detected during the CERCLA hazardous waste disposal site investigations. Modification of the current RCRA program to include routine analysis for volatile organic compounds would correct this weakness.     

Vadose zone-attenuated artificial recharge for input to a ground water model

Accurate representation of artificial recharge is requisite to calibration of a ground water model of an unconfined aquifer for a semiarid or arid site with a vadose zone that imparts significant attenuation of liquid transmission and substantial anthropogenic liquid discharges. Under such circumstances, artificial recharge occurs in response to liquid disposal to the vadose zone in areas that are small relative to the ground water model domain. Natural recharge, in contrast, is spatially variable and occurs over the entire upper boundary of a typical unconfined ground water model. An improved technique for partitioning artificial recharge from simulated total recharge for inclusion in a ground water model is presented. The improved technique is applied using data from the semiarid Hanford Site. From 1944 until the late 1980s, when Hanford's mission was the production of nuclear materials, the quantities of liquid discharged from production facilities to the ground vastly exceeded natural recharge. Nearly all hydraulic head data available for use in calibrating a ground water model at this site were collected during this period or later, when the aquifer was under the diminishing influence of the massive water disposals. The vadose zone is typically 80 to 90 m thick at the Central Plateau where most production facilities were located at this semiarid site, and its attenuation of liquid transmission to the aquifer can be significant. The new technique is shown to improve the representation of artificial recharge and thereby contribute to improvement in the calibration of a site-wide ground water model.     

The Geochemistry of Boron in a Landfill Monitoring Program

Ground water monitoring data collected during the past eight years at a permitted municipal solid waste (MSW) disposal facility located in the midwestern United States indicated fluctuations in typical leachate indicator parameter concentrations. Apparent trends in the data inferred leachate outbreak, generating suspicion as to the integrity of the landfill liner. Eight ground water monitoring wells were installed in three distinct geologic units at the landfill facility, including glacial drift, silurian dolomite, and a post-glacial peat fen, which is downgradient from the landfill. Piezometer nests were used to define ground water gradients at the site. Using boron as an indicator, the occurrence of analytes of concern in the downgradient monitoring wells were shown to be indicative of the natural geochemistry of site ground water. This work emphasizes the importance of understanding site hydrogeology during the interpretation of ground water quality data.     

Analysis of Water Saturation, NAPL Content, Degradation Half-Life, and Lower Boundary Conditions on VOC Transport Modeling: Implications for Closure of Soil Venting Systems

Simulations using a one-dimensional, analytical, vadose zone, solute-transport screening code (VFLUX) were conducted to assess the effect of water saturation, NAPL saturation, degradation half-life, and boundary conditions at the vadose zone/ground water interface on model output. At high initial soil concentrations, model output was significantly affected by input parameters and lower boundary conditions yet still resulted in consistent decision-making to initiate or continue venting application. At lower soil concentrations, however, typical of what is observed after prolonged venting application, differences in model input and selection of lower boundary conditions resulted in inconsistent decision-making. Specifically, under conditions of low water saturation, use of a first-type, time-dependent lower boundary condition indicated that the primary direction of mass flux was from ground water to the vadose zone, suggesting little benefit from continued venting application. Use of a finite, zero-gradient lower boundary condition, though, indicated continued mass flux from the vadose zone to ground water, suggesting a continued need for venting application. In this situation, sensitivity analysis of input parameters, selection of boundary conditions, and consideration of overall objectives in vadose zone modeling become critical in regulatory decision-making.     

A Diffusive Sampler for Passive Monitoring of Underground Storage Tanks

Passive measurements of volatile organic compounds (VOCs) provide a method for early detection and long-term monitoring of potential leaks from underground storage tanks (USTs) and associated fuel service lines. A diffusive sampler was constructed of a sorbent tube that fits inside a specially designed sampling chamber. VOCs in the soil enter the chamber by molecular diffusion and are collected by the sorbent. The sorbent is easily retrieved for laboratory analyses by thermally desorbing into a gas chromatograph/mass spectrometer (GC/MS), or qualitative concentrations can be determined directly in the field with specific-indicator detectors.
The diffusive samplers were evaluated in an exposure chamber under controlled conditions. Laboratory measurements of the sorbed mass of organic vapor were found to be in close agreement with theoretical values and indicate the passive sampling approach is viable for detecting relatively low concentrations of organic vapors in the vadose zone over a one-day sampling period, as well as providing relatively long-term monitoring periods up to 58 days. A field test found the sampling approach successful in identifying an area where the vadose zone was contaminated by leaking petroleum USTs.     

A Method to Evaluate the Vertical Distribution of VOCs in Ground Water in a Single Borehole

Volatile organic compounds (VOCs) are present in multiple water-bearing zones beneath and downgradient of Lawrence Livermore National Laboratory. This area is composed of interfingering unconsolidated alluvial sediments with hydraulic conductivities ranging over four orders of magnitude. The more permeable sediments exhibit moderate hydraulic interconnection horizontally and less interconnection vertically, and appear to consist largely of interconnected stream channel deposits. To optimize selection of monitoring well screened intervals in this complex environment, a technique that enables collection of saturated formation samples from each water-bearing zone without contamination from other VOC-containing zones was developed, tested, and implemented. The technique utilizes a wireline punch-coring system that allows the drill bit to be replaced with a core barrel without removing the drill rod from the borehole. To help ensure that a sample from one water-bearing zone is not contaminated by VOCs from another zone, the drilling fluid is replaced with new fluid before each sampling run. Overnight chemical analysis by gas chromatography enables field personnel to know the vertical distribution of VOCs as drilling proceeds. Since its first use in 1985, the technique has successfully characterized the presence or absence of VOCs in ground water in 123 of 140 wells, many with concentrations in ground water in the low parts-per-billion range. Our sampling technique is a cost-effective and rapid method of evaluating the vertical distribution of VOCs in ground water in a complex hydrogeologic environment.     

Electrical resistance tomography experiments at the Oregon Graduate Institute

Three controlled experiments were conducted at the Oregon Graduate Institute (OGI) with the purpose of evaluating electrical resistance tomography for imaging underground processes associated with in-situ site assessment and remediation. The OGI facilities are unique: a double-wall tank 10 m square and 5 m deep, filled with river bottom sediments and instrumented for geophysical and hydrological studies. At this facility, liquid contaminants could be released into the confined soil at a scale sufficiently large to represent real-world physical phenomena.In the first test, images of electrical resistivity were made before and during a controlled spill of gasoline into a sandy soil. The primary purpose was to determine if electrical resistivity images could detect the hydrocarbon in either the vadose or saturated zone. Definite changes in electrical resistivity were observed in both the vadose and saturated soils. The effects were an increase in resistivity of as much as 10% above pre-release values. A single resistive anomaly was imaged, directly below the release point, principally within the vadose zone but extending below the phreatic surface. The anomaly remained identifiable in tomograms taken two days after the release ended with clear indications of lateral spreading along the water table.The second test involved electrical resistance measurements before, during, and after air sparging in a saturated soil. The primary purpose was to determine if the electrical images could be used to detect and delineate the extent of the zone influenced by sparging. The images showed an increase of about 20% in resistivity over background values within the sparged zone and the extent of the imaged zone agreed with that inferred from other information.Electrical resistivity tomography measurements were made under a simulated oil storage tank in the third test. Comparison of images taken before and during separate releases of brine and water showed effects of changes induced by the water or brine. The simulated leak and its location were imaged as a conductive anomaly centered near the point of origin and were observed to spread with time during the release.     

Sampling VOCs with Porous Suction Samplers in the Presence of Ethanol: How Much Are We Losing?

Porous suction samplers have been widely used to obtain ground water samples from the vadose zone. However, previous studies identified different mechanisms that may compromise the sample's representativeness, such as volatilization and sorption. This issue is particularly important when dealing with volatile organic compounds (VOCs) as in gasoline spills. Ethanol is common in modern fuels and so may be present in ground water contamination from fuel releases. The objective of this work was to evaluate the losses of VOCs in the presence of ethanol when using porous suction samplers. Laboratory experiments were performed using a ceramic porous suction sampler to sample test solution containing benzene, toluene, xylenes, trimethylbenzenes, naphthalene, and different volumetric fractions of ethanol. Significant losses were found up to 30% for ethylbenzene. Ethanol was found to affect the accuracy of the readings by two main mechanisms: first, negatively, by increasing the headspace in the sampling tube, and second, positively, increasing partition to the aqueous phase due to the cosolvent effect and therefore decreasing the mass loss by volatilization. As a consequence, the highest losses of VOCs were found at intermediate ethanol volume fractions: 10% and 20% (v/v). The losses can be anticipated by measuring the ratio of gas to water in the sampling line and then by applying simple partition models considering cosolvency by ethanol. The importance of adequate purging when using porous suction samplers was also shown.     

Equipment Decontamination Procedures for Ground Water and Vadose Zone Monitoring Programs: Status and Prospects

A major portion of the work effort and, therefore, the money spent during investigations of ground water and the vadose zone at hazardous waste sites is associated with collecting chemical data. To that end, effective decontamination of reusable drilling equipment, sampling apparatus, and tools is critical to the credibility of chemical data. Samples representative of the site under study are essential.
Several state and federal regulatory agencies have established guidelines for procedures that should be considered when developing decontamination protocols. These agencies were contacted and asked to furnish copies of their decontamination guidelines. The information received was reviewed, and comparisons were made to assess the status of standards of decontamination practices for ground water and vadose zone monitoring programs at hazardous waste sites. Summaries of a variety of decontamination protocols were prepared. From this review, it is apparent that there is a need to standardize, to the extent possible, procedures for the field decontamination of equipment.
Two ASTM Subcommittees, D18.14 on Waste Management and D18.21 on Ground Water and Vadose Zone Monitoring, are currently working on developing standards for decontamination procedures. They, in cooperation with state and federal agencies and other interested technical groups, will develop standards for the field decontamination of equipment used to study ground water and the vadose zone.     

Characterising deep vadose zone water movement and solute transport under typical irrigated cropland in the North China Plain

Understanding the dynamics and mechanisms of soil water movement and solute transport is essential for accurately estimating recharge rates and evaluating the impacts of agricultural activities on groundwater resources. In a thick vadose zone (0–15 m) under irrigated cropland in the piedmont region of the North China Plain, soil water content, matric potential, and solute concentrations were measured. Based on these data, the dynamics of soil water and solutes were analysed to investigate the mechanisms of soil water and solute transport. The study showed that the 0–15‐m vadose zone can be divided into three layers: an infiltration and evaporation layer (0–2 m), an unsteady infiltration layer (2–6 m), and a quasi‐steady infiltration layer (6–15 m). The chloride, nitrate, and sulphate concentrations all showed greater variations in the upper soil layer (0–1 m) compared to values in the deep vadose zone (below 2 m). The average concentrations of these three anions in the deep vadose zone varied insignificantly with depth and approached values of 125, 242, and 116 mg/L. The accumulated chloride, sulphate, and nitrate were 2,179 ± 113, 1,760 ± 383, and 4,074 ± 421 kg/ha, respectively. The soil water potential and solute concentrations indicated that uniform flow and preferential flow both occurred in the deep vadose zone, and uniform flow was the dominant mechanism of soil water movement in this study. The piston‐like flow velocity of solute transport was 1.14 m per year, and the average value of calculated leached nitrate nitrogen was 107 kg/ha?year below the root zone. The results can be used to better understand recharge processes and improve groundwater resources management.