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.     

Analysis of Soil Vapor Extraction Data to Evaluate Mass-Transfer Constraints and Estimate Source-Zone Mass Flux

Methods are developed to use data collected during cyclic operation of soil vapor extraction (SVE) systems to help characterize the magnitudes and time scales of mass flux associated with vadose zone contaminant sources. Operational data collected at the Department of Energy’s Hanford site are used to illustrate the use of such data. An analysis was conducted of carbon tetrachloride vapor concentrations collected during and between SVE operations. The objective of the analysis was to evaluate changes in concentrations measured during periods of operation and nonoperation of SVE, with a focus on quantifying temporal dynamics of the vadose zone contaminant mass flux, and associated source strength. Three mass flux terms, representing mass flux during the initial period of an SVE cycle, during the asymptotic period of a cycle, and during the rebound period, were calculated and compared. It was shown that it is possible to use the data to estimate time frames for effective operation of an SVE system if a sufficient set of historical cyclic operational data exists. This information could then be used to help evaluate changes in SVE operations, including system closure. The mass flux data would also be useful for risk assessments of the impact of vadose zone sources on groundwater contamination or vapor intrusion.     

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.     

1,4‐Dioxane Soil Remediation Using Enhanced Soil Vapor Extraction: I. Field Demonstration

1,4‐Dioxane is totally miscible in water, sequestering in vadose pore water that can serve as a source of long‐term groundwater contamination. Although some 1,4‐dioxane is removed by conventional soil vapor extraction (SVE), remediation is typically inefficient. SVE efficiency is hindered by low Henry’s Law constants at ambient temperature and redistribution to vadose pore water if SVE wells pull 1,4‐dioxane vapors across previously clean soil. It was hypothesized that heated air injection and more focused SVE extraction (“Enhanced SVE” or XSVE) could increase the efficiency of 1,4‐dioxane vadose treatment, and this new process was tested at former McClellan Air Force Base, CA. The XSVE system had four peripheral heated air injection wells surrounding a 6.1 m × 6.1 m × 9.1 m deep treatment zone with a central vapor extraction well. After 14 months of operation, soil temperatures reached as high as ~90 °C near the injection wells and the treatment zone was flushed with ~20,000 pore volumes of injected air. Post‐treatment sampling results showed reductions of ~94% in 1,4‐dioxane and ~45% in soil moisture. Given the simplicity of the remediation system components and the promising demonstration test results, XSVE has the potential to be a cost‐effective remediation option for vadose zone soil containing 1,4‐dioxane.     

Influence of Soil Air Permeability Change on Soil Vapour Extraction Systems Design

Soil air permeability plays a decisive role in the effectiveness of soil vapour extraction (SVE) for the removal of volatile organic contaminants (VOCs) from soil. The objective of this work is to study the change of the soil air permeability during continuous venting and removal of contaminant from a polluted soil. SVE pilot experiments were conducted to investigate the interaction of soil air permeability with total liquids saturation. Oppositely to previous studies, air permeability was measured by fitting pressure data measured in a 3D laboratory venting pilot to an analytical airflow solution. The experimental correlation was compared with two different correlations published previously. A difference was observed between measured and calculated air relative air permeabilities especially for low water saturation degrees. The importance of the correct estimate of relative permeability was then illustrated by comparing vacuums and streamlines calculated using measured permeability and permeability values estimated with the two correlations tested here. Results show that an inappropriate assessment of relative permeability may engender significant errors in designing an SVE system. The second part of this work reports on the influence of air permeability change on the prediction capability of an SVE mathematical model. A significant difference between simulated breakthrough curves, estimated using firstly the relationship established experimentally and secondly the two other correlations, was observed. These results lead us to say that inadequate characterization of the air permeability change may generate significant errors in removal rate and closure time estimates.     

Multimedia Risk-Based Soil Cleanup at a Gasoline-Contaminated Site Using Vapor Extraction

At a utility service center, gasoline from an underground storage tank had leaked into subsurface vadose zone soils for several years. To remediate the site, a soil vapor extraction (SVE) system was installed and operated. At the completion of the SVE operation, gasoline-containing residues in several confirmation soil borings exceeded agency-mandated cleanup levels. Rather than continue with SVE, a risk-based approach was developed to evaluate what levels of gasoline-containing residues could be left in the soil and still protect human health. The risk-based approach consisted of simulating the fate of chemical residues through the vadose zone and then into both the ground water and atmosphere. Receptor point concentrations were predicted, and health risks were assessed. The risk assessment concluded that ingestion of contaminated ground water and inhalation of air while showering were the largest potential contributors to risk, and that risks associated with inhalation of vapor-containing ambient air are small. However, all predicted risks are below the acceptable risk levels of 10⁻⁶ individual cancer risk probability and 1.0 hazard index. Therefore, the lead agency accepted the recommendation that the site requires no further remediation. The service center continues normal operations today.     

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.     

1,4‐Dioxane Soil Remediation Using Enhanced Soil Vapor Extraction (XSVE): II. Modeling

1,4‐Dioxane is a volatile organic compound that is fully miscible in water, allowing it to sequester in vadose zone pore water and serve as a long‐term source of groundwater contamination. Conventional soil vapor extraction (SVE) removes 1,4‐dioxane; however, substantial 1,4‐dioxane can remain even after other colocated chlorinated solvents have been remediated. A field demonstration of “enhanced SVE” (XSVE) with focused extraction and heated injection was conducted at former McClellan AFB, CA, achieving 94% reduction in soil concentrations. A screening‐level tool, HypeVent XSVE, was created to assist in system design and data reduction and to anticipate how operating factors affect XSVE performance (e.g., cleanup level, remediation time, etc.). It assumes well‐mixed conditions, and combines an energy balance, mass balances for water and contaminant, and a temperature‐dependent 1,4‐dioxane Henry's Law constant. User inputs include the target treatment zone size, initial 1,4‐dioxane and soil moisture concentrations, and ambient site and injection/extraction conditions (temperature, humidity). Projections based on inputs representative of demonstration site conditions adequately anticipated the observed macroscopic field results. Sensitivity analyses show that removal increases with increasing heated air injection temperature and relative humidity and decreasing initial soil moisture content.     

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

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

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.     

Non-isothermal soil water transport and evaporation

A detailed model was formulated to describe the non-isothermal transport of water in the unsaturated soil zone. The model consists of the coupled equations of mass conservation for the liquid phase, gas phase and water vapor and the energy conservation equation. The water transport mechanisms considered are convection in the liquid phase, and convection, diffusion and dispersion of vapor in the gas phase. The boundary conditions at the soil–atmosphere interface include dynamical mass flux and energy flux that accounts for radiation transport. Comparison of numerical simulations results with published experimental data demonstrated that the present model is able to describe water and energy transport dynamics, including situations of low and moderate soil moisture contents. Analysis of field studies on soil drying suggests that that dispersion flux of the water vapor near the soil surface, which is seldom considered in soil drying models, can make a significant contribution to the total water flux.     

A Practical Approach to the Design, Operation, and Monitoring of In Situ Soil-Venting Systems

When operated properly, in situ soil venting or vapor extraction can be one of the most cost-effective remediation processes for soils contaminated with gasoline, solvents, or other relatively, volatile compounds. The components of soil-venting systems are typically off-the-shelf items, and the installation of wells and trenches can be done by reputable environmental firms. However, the design, operation, and monitoring of soil-venting systems are not trivial. In fact, choosing whether or not venting should be applied at a given site is a difficult decision in itself. If one decides to utilize venting, design criteria involving the number of wells, well spacing, well location, well construction, and vapor treatment systems must be addressed. A series of questions must be addressed to decide if venting is appropriate at a given site and to design cost-effective in situ soil-venting systems. This series of steps and questions forms a "decision tree" process. The development of this approach is an attempt to identify the limitations of in situ soil venting, and subjects or behavior that are currently difficult to quantify and for which future study is needed.     

Characterization of Persistent Volatile Contaminant Sources in the Vadose Zone

Effective long‐term operation of soil vapor extraction (SVE) systems for cleanup of vadose‐zone sources requires consideration of the likelihood that remediation activities over time will alter the subsurface distribution and configuration of contaminants. A method is demonstrated for locating and characterizing the distribution and nature of persistent volatile organic contaminant (VOC) sources in the vadose zone. The method consists of three components: analysis of existing site and SVE‐operations data, vapor‐phase cyclic contaminant mass‐discharge testing, and short‐term vapor‐phase contaminant mass‐discharge tests conducted in series at multiple locations. Results obtained from the method were used to characterize overall source zone mass‐transfer limitations, source‐strength reductions, potential changes in source‐zone architecture, and the spatial variability and extent of the persistent source(s) for the Department of Energy's Hanford site. The results confirmed a heterogeneous distribution of contaminant mass discharge throughout the vadose zone. Analyses of the mass‐discharge profiles indicate that the remaining contaminant source is coincident with a lower‐permeability unit at the site. Such measurements of source strength and size as obtained herein are needed to determine the impacts of vadose‐zone sources on groundwater contamination and vapor intrusion, and can support evaluation and optimization of the performance of SVE operations.     

Groundwater remediation: the next 30 years

Groundwater remediation technologies are designed, installed, and operated based on the conceptual models of contaminant hydrogeology that are accepted at that time. However, conceptual models of remediation can change as new research, new technologies, and new performance data become available. Over the past few years, results from multiple-site remediation performance studies have shown that achieving drinking water standards (i.e., Maximum Contaminant Levels, MCLs) at contaminated groundwater sites is very difficult. Recent groundwater research has shown that the process of matrix diffusion is one key constraint. New developments, such as mass discharge, orders of magnitude (OoMs), and SMART objectives are now being discussed more frequently by the groundwater remediation community. In this paper, the authors provide their perspectives on the existing "reach MCLs" approach that has historically guided groundwater remediation projects, and advocate a new approach built around the concepts of OoMs and mass discharge.     

Methodology for comparing source and plume remediation alternatives

It is often difficult at contaminated sites to decide whether remediation effort should be focused on the contaminant source, the dissolved plume, or on both zones. The decision process at these sites is hampered by a lack of quantitative tools for comparing remediation alternatives. A new screening-level mass balance approach is developed for simulating the transient effects of simultaneous ground water source and plume remediation. The contaminant source model is based on a power function relationship between source mass and source discharge, and it can consider partial source remediation at any time after the initial release. The source model serves as a time-dependent mass flux boundary condition to a new analytical plume model, where flow is assumed to be one dimensional, with three-dimensional dispersion. The plume model simulates first-order sequential decay and production of several species, and the decay rates and parent/daughter yield coefficients are variable functions of time and distance. This new method allows for flexible simulation of natural attenuation or remediation efforts that enhance plume degradation. The plume remediation effort may be temporary or delayed in time, limited in space, and it may have different chemical effects on different contaminant species in the decay chain.     

Soil Gas Sampling for 1,4‐Dioxane during Heated Soil Vapor Extraction

Soil gas sampling for 1,4‐dioxane at elevated soil temperatures, such as those experienced during in‐situ thermal treatment, has the potential to yield low results due to condensation of water vapor in the ambient temperature sampling vessel and the partitioning of 1,4‐dioxane into that condensate. A simple vapor/condensate sampling apparatus was developed to collect both condensate and vapor samples to allow for determination of a reconstituted effective soil gas concentration for 1,4‐dioxane. Results using the vapor/condensate sampling apparatus during a heated air injection SVE field demonstration are presented, along with those of a comparable laboratory system. Substantial 1,4‐dioxane mass was found in the condensate in both the lab and field (as high as ~50% in field). As soil temperatures increased, less 1,4‐dioxane mass was detected in field condensate samples than expected based on laboratory experiments. Extraction well effluent sampling at the wellhead by direct vapor canister sampling provided erratic results (several biased low by a factor of 5 or more) compared to those of the vapor/condensate apparatus. Direct vapor canister sampling of extraction well effluent after the air‐water separator, however, provided results reasonably comparable (within 35%) to those using the vapor/condensate apparatus at the wellhead. Soil gas sampling at elevated temperatures using the vapor/condensate apparatus alleviates potential low sampling bias due to condensation.     

A Rapid Decision Support Tool for Estimating Impacts of a Vadose Zone Volatile Organic Compound Source on Groundwater and Soil Gas

Diminishing rates of subsurface volatile contaminant removal by soil vapor extraction (SVE) oftentimes warrants an in-depth performance assessment to guide remedy decision-making processes. Such a performance assessment must include quantitative approaches to better understand the impact of remaining vadose zone contamination on soil gas and groundwater concentrations. The spreadsheet-based Soil Vapor Extraction Endstate Tool (SVEET) software functionality has recently been expanded to facilitate quantitative performance assessments. The updated version, referred to as SVEET2, includes expansion of the input parameter ranges for describing a site (site geometry, source characteristics, etc.), an expanded list of contaminants, and incorporation of elements of the Vapor Intrusion Estimation Tool for Unsaturated-zone Sources software to provide soil gas concentration estimates for use in vapor intrusion evaluation. As part of the update, SVEET2 was used to estimate the impact of a tetrachloroethene (PCE) vadose zone source on groundwater concentrations, comparing SVEET2 results to field-observed values at an undisclosed site where SVE was recently terminated. PCE concentrations from three separate monitoring wells were estimated by SVEET2 to be within the range of 6.0–6.7 μg/L, as compared to actual field concentrations that ranged from 3 to 11 μg/L PCE. These data demonstrate that SVEET2 can rapidly provide representative quantitative estimates of impacts from a vadose zone contaminant source at field sites. In the context of the SVE performance assessment, such quantitative estimates provide a basis to support remedial and/or regulatory decisions regarding the continued need for vadose zone volatile organic compound remediation or technical justification for SVE termination, which can significantly reduce the cost to complete for a site.     

A Surface-Flux Measurement Method for Screening Contamination from Volatile Organic Compounds

Measurement of the vapor flux from volatile organic compounds (VOCs) provides a rapid means for screening large areas of potential contamination. The vapor flux is determined from the rate of VOC concentration buildup inside a 3.1L accumulator device that is sealed to the surface of the contaminated soil. After the VOC concentrations are allowed to increase for a few minutes, they are analyzed with a portable gas chromatograph or a total organic vapor analyzer.
The measurement approach was evaluated at a field site in an area where the ground water and soil had been impacted with Jet Fuel No. 4 (JP-4). An indication of the areal extent of impact was determined by mapping the surface VOC vapor flux. The pattern revealed by the flux measurements was found to coincide, in rough outline, with the known extent of toluene concentrations in the ground water and with conventional soil-gas survey results. In addition, a mathematical model describing VOC diffusion into the accumulator device was verified by performing laboratory measurements of the surface VOC vapor flux on a sandbox designed to simulate a hazardous waste site.     

Case History of a Large-Scale Air Sparging/Soil Vapor Extraction System for Remediation of Chlorinated Volatile Organic Compounds in Ground Water

A large-scale air sparging/soil vapor extraction (AS/SVE) project constructed within coastal plain sediments in New Jersey has demonstrated substantial progress toward remediating ground water through removal of volatile organic compounds (VOCs). Potential concerns identified prior to project implementation regarding hydraulic mounding, reduction in hydraulic conductivity, development of air channels, and the absence of hydraulic containment were assessed and addressed through testing and operational features incorporated into the project. At the project site, AS/SVE has successfully reduced the presence of many VOCs to undetectable levels, while reducing the concentrations of the remaining VOCs by factors of two to 500. The physical agitation caused by air sparging, and incomplete transformation from sorbed and nonaqueous phases to the vapor phase, appears to temporarily increase VOC concentrations and/or mobility of dense nonaqueous phase liquids (DN APLs) within source areas at the project site, but this is addressed in terms of subsequent removal of VOCs by properly placed downgradient treatment lines and VOCs by properly placed downgradient treatment lines and DNAPL recovery wells. This case study identifies and evaluates project-specific features and provides empirical data for potential comparison to other candidates AS/SVE sites.     

Field Study of Soil Vapor Extraction for Reducing Off-Site Vapor Intrusion

Soil vapor extraction (SVE) is effective for removing volatile organic compound (VOC) mass from the vadose zone and reducing the potential for vapor intrusion (VI) into overlying and surrounding buildings. However, the relationship between residual mass in the subsurface and VI is complex. Through a series of alternating extraction (SVE on) and rebound (SVE off) periods, this field study explored the relationship and aspects of SVE applicable to VI mitigation in a commercial/light-industrial setting. The primary objective was to determine if SVE could provide VI mitigation over a wide area encompassing multiple buildings, city streets, and subsurface utilities and eliminate the need for individual subslab depressurization systems. We determined that SVE effectively mitigates offsite VI by intercepting or diluting contaminant vapors that would otherwise enter buildings through foundation slabs. Data indicate a measurable (5 Pa) influence of SVE on subslab/indoor pressure differential may occur but is not essential for effective VI mitigation. Indoor air quality improvements were evident in buildings 100 to 200 feet away from SVE including those without a measurable reversal of differential pressure across the slab or substantial reductions in subslab VOC concentration. These cases also demonstrated mitigation effects across a four-lane avenue with subsurface utilities. These findings suggest that SVE affects distant VI entry points with little observable impact on differential pressures and without relying on subslab VOC concentration reductions.