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.     

Source Screening Module for Contaminant Transport Analysis Through Vadose and Saturated Zones

At complex sites there may be many potential sources of contaminants within the vadose zone. Screening‐level analyses are useful to identify which potential source areas should be the focus of detailed investigation and analysis. A source screening module (SSM) has been developed to support preliminary evaluation of the threat posed by vadose zone waste sites on groundwater quality. This tool implements analytical solutions to simulate contaminant transport through the unsaturated and saturated zones to predict time‐varying concentrations at potential groundwater receptors. The SSM integrates several transport processes in a single simulation that is implemented within a user‐friendly, Microsoft Excel? ‐ based interface.     

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.     

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.     

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.     

Estimating the Impact of Vadose Zone Sources on Groundwater to Support Performance Assessment of Soil Vapor Extraction

Soil vapor extraction (SVE) is a prevalent remediation remedy for volatile organic compound (VOC) contaminants in the vadose zone. To support selection of an appropriate condition at which SVE may be terminated for site closure or for transition to another remedy, an evaluation is needed to determine whether vadose zone VOC contamination has been diminished sufficiently to keep groundwater concentrations below threshold values. A conceptual model for this evaluation was developed for VOC fate and transport from a vadose zone source to groundwater when vapor‐phase diffusive transport is the dominant transport process. A numerical analysis showed that, for these conditions, the groundwater concentration is controlled by a limited set of parameters, including site‐specific dimensions, vadose zone properties, and source characteristics. On the basis of these findings, a procedure was then developed for estimating groundwater concentrations using results from the three‐dimensional multiphase transport simulations for a matrix of parameter value combinations and covering a range of potential site conditions. Interpolation and scaling processes are applied to estimate groundwater concentrations at compliance (monitoring) wells for specific site conditions of interest using the data from the simulation results. The interpolation and scaling methodology using these simulation results provides a far less computationally intensive alternative to site‐specific three‐dimensional multiphase site modeling, while still allowing for parameter sensitivity and uncertainty analyses. With iterative application, the approach can be used to consider the effect of a diminishing vadose zone source over time on future groundwater concentrations. This novel approach and related simulation results have been incorporated into a user‐friendly Microsoft® Excel®‐based spreadsheet tool entitled SVEET (Soil Vapor Extraction Endstate Tool), which has been made available to the public.     

Vadose Zone Monitoring: An Early Warning System

Currently, vadose zone monitoring is required under the Resource Conservation and Recovery Act (RCRA) only at land treatment facilities. Contaminant leak detection through ground water monitoring is very important, but it is considered to be after the fact. Remedial action costs can be reduced considerably by monitoring the vadose zone for compounds that exhibit high rates of movement. Volatile organic compounds (VOCs) exhibit this property and are present at many municipal landfills, recycling facilities, and treatment storage and disposal facilities (TSDFs). Through the authors'personal experience, it has been noted that gaseous phase transport of VOCs through the vadose zone is at least an order of magnitude greater than advective transport of VOCs in ground water. Therefore, VOCs in soil gas are an effective early warning leak detection parameter. Downward movement of leachate can be intercepted by porous cup lysimeters. Attenuation in the vadose zone slows the apparent movement of contaminants; however, it is only a matter of time before leachate reaches the water table. The authors believe that soil-gas and pore-water monitoring should and eventually will be required at all RCRA sites. If vadose zone monitoring becomes an additional requirement under RCRA, both the facility owner and the taxpayer will benefit. During the interim, facility owners can benefit by employing vadose zone monitoring techniques coupled with either qualitative or quantitative chemical analyses.     

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.     

The influence of dimensionality on simulations of mass recovery from nonuniform dense non-aqueous phase liquid (DNAPL) source zones

The influence of model dimensionality on predictions of mass recovery from dense non-aqueous phase liquid (DNAPL) source zones in nonuniform permeability fields was investigated using a modified version of the modular three-dimensional transport simulator (MT3DMS). Thirty-two initial two- (2D) and three-dimensional (3D) tetrachloroethene–DNAPL source zone architectures, taken from a recent modeling study, were used as initial conditions for this analysis. Commonly employed source zone metrics were analyzed to determine differences between 2D and 3D predictions: (i) down-gradient flux-averaged contaminant concentration, (ii) reductions in contaminant mass flux through a down-gradient boundary, (iii) source zone ganglia-to-pool (GTP) ratio, and (iv) time required to achieve a remediation objective. 3D flux-averaged contaminant concentrations were approximately 3.5 times lower than concentrations simulated in 2D. This difference was attributed to dilution of the contaminant concentrations down gradient of the source zone. Contaminant flux reduction predictions for a given mass recovery were generally 5% higher in 3D simulations than in 2D simulations. The GTP ratio declined over time as mass was recovered in both 2D and 3D simulations. Although the source longevity (i.e., time required to achieve 99.99% mass recovery) differed between individual 2D and 3D realizations, the mean source longevity for the 2D and 3D simulation ensembles was within 2%. 2D simulations tended to over-predict the time required to achieve lower mass recovery levels (e.g. 50% mass recovery) due to a smaller contaminated area exposed to uncontaminated water. These findings suggest that ensemble averages of 2D numerical simulations of DNAPL migration, entrapment, dissolution, and mass recovery in statistically homogenous, nonuniform media may provide reasonable approximations to average behavior obtained using simulations conducted in fully three-dimensional domains.     

Comparisons of diffusive and advective fluxes of gas phase volatile organic compounds (VOCs) in unsaturated zones under natural conditions

Diffusive flux is traditionally treated as the dominant mechanism of gas transport in unsaturated zones under natural conditions, and advective flux is usually neglected. However, some researchers have found that pressure-driven and density-driven advective flux may also be significant under certain conditions. This article compares the diffusive, pressure-driven and density-driven advective fluxes of gas phase volatile organic compound (VOCs) in unsaturated zones under various natural conditions. The presence of a less or more permeable layer at ground surface in a layered unsaturated zone is investigated for its impact on the net contribution of advective and diffusive fluxes. Results show although the transient advective flux can be greater than the diffusive flux, under most of the field conditions the net contribution of the advective flux is one to three orders of magnitude less than the diffusive flux, and the influence of the density-driven flux is undetectable. The advective flux contributes comparably with the diffusive flux only when the gas-filled porosity is less than 0.05. The presence of a less permeable layer at ground surface slightly increases the total flux in the underlying layer, while the presence of a more permeable layer at ground surface significantly increases the total flux in it. When the magnitude of water table fluctuation is less than 1 cm, and the period is greater than 0.5 day, the fluctuation of the water table can be simulated by fixing the water table position and setting a fluctuating moving velocity at the water table.     

Evaluation of Mass Flux to and from Ground Water Using a Vertical Flux Model (VFLUX): Application to the Soil Vacuum Extraction Closure Problem

Site closure for soil vacuum extraction (SVE) application typically requires attainment or specified soil concentration standards based on the premise that mass flux from the vadose zone to ground water not result in levels exceeding maximum contaminant levels (MCLs). Unfortunately, realization of MCLs in ground water may not be attainable at many sites. This results in soil remediation efforts that may be in excess of what is necessary for future protection of ground water and soil remediation goals which often cannot be achieved within a reasonable time period. Soil venting practitioners have attempted to circumvent these problems by basing closure on some predefined percent total mass removal, or an approach to a vapor concentration asymptote. These approaches, however, are subjective and influenced by venting design. We propose an alternative strategy based on evaluation of five components: (1) site characterization, (2) design. (3) performance monitoring, (4) rule-limited vapor transport, and (5) mass flux to and from ground water. Demonstration of closure is dependent on satisfactory assessment of all five components. The focus of this paper is to support mass flux evaluation. We present a plan based on monitoring of three subsurface zones and develop an analytical one-dimensional vertical flux model we term VFLUX. VFLUX is a significant improvement over the well-known numerical one-dimensional model. VLEACH, which is often used for estimation of mass flux to ground water, because it allows for the presence of nonaqueous phase liquids (NAPLs) in soil, degradation, and a lime-dependent boundary condition at the water table inter-face. The time-dependent boundary condition is the center-piece of our mass flux approach because it dynamically links performance of ground water remediation lo SVE closure. Progress or lack of progress in ground water remediation results in either increasingly or decreasingly stringent closure requirements, respectively.     

A Coupled Groundwater–Surface Water Modeling Framework for Simulating Transition Zone Processes

There is an identified need for fully representing groundwater–surface water transition zone (i.e., the sediment zone that connects groundwater and surface water) processes in modeling fate and transport of contaminants to assist with management of contaminated sediments. Most existing groundwater and surface water fate and transport models are not dynamically linked and do not consider transition zone processes such as bioturbation and deposition and erosion of sediments. An interface module is developed herein to holistically simulate the fate and transport by coupling two commonly used models, Environmental Fluid Dynamics Code (EFDC) and SEAWAT, to simulate surface water and groundwater hydrodynamics, while providing an enhanced representation of the processes in the transition zone. Transition zone and surface water contaminant processes were represented through an enhanced version of the EFDC model, AQFATE. AQFATE also includes SEDZLJ, a state‐of‐the‐science surface water sediment transport model. The modeling framework was tested on a published test problem and applied to evaluate field‐scale two‐ and three‐dimensional contaminant transport. The model accurately simulated concentrations of salinity from a published test case. For the field‐scale applications, the model showed excellent mass balance closure for the transition zone and provided accurate simulations of all transition zone processes represented in the modeling framework. The model predictions for the two‐dimensional field case were consistent with site‐specific observations of contaminant migration. This modeling framework represents advancement in the simulation of transition zone processes and can help inform risk assessment at sites where contaminant sources from upland areas have the potential to impact sediments and surface water.     

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.     

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.     

Modeling surface and ground water mixing in the hyporheic zone using MODFLOW and MT3D

We used a three-dimensional MODFLOW model, paired with MT3D, to simulate hyporheic zones around debris dams and meanders along a semi-arid stream. MT3D simulates both advective transport and sink/source mixing of solutes, in contrast to particle tracking (e.g. MODPATH), which only considers advection. We delineated the hydrochemically active hyporheic zone based on a new definition, specifically as near-stream subsurface zones receiving a minimum of 10% surface water within a 10-day travel time. Modeling results indicate that movement of surface water into the hyporheic zone is predominantly an advective process. We show that debris dams are a key driver of surface water into the subsurface along the experimental reach, causing the largest flux rates of water across the streambed and creating hyporheic zones with up to twice the cross-sectional area of other hyporheic zones. Hyporheic exchange was also found in highly sinuous segments of the experimental reach, but flux rates are lower and the cross-sectional areas of these zones are generally smaller. Our modeling approach simulated surface and ground water mixing in the hyporheic zone, and thus provides numerical approximations that are more comparable to field-based observations of surface–groundwater exchange than standard particle-tracking simulations.     

Implementation of Solute Transport in the Vadose Zone into the “HYDRUS Package for MODFLOW”

The “HYDRUS package for MODFLOW” is an existing MODFLOW package that allows MODFLOW to simultaneously evaluate transient water flow in both unsaturated and saturated zones. The package is based on incorporating parts of the HYDRUS-1D model (to simulate unsaturated water flow in the vadose zone) into MODFLOW (to simulate saturated groundwater flow). The coupled model is effective in addressing spatially variable saturated-unsaturated hydrological processes at the regional scale. However, one of the major limitations of this coupled model is that it does not have the capability to simulate solute transport along with water flow and therefore, the model cannot be employed for evaluating groundwater contamination. In this work, a modified unsaturated flow and transport package (modified HYDRUS package for MODFLOW and MT3DMS) has been developed and linked to the three-dimensional (3D) groundwater flow model MODFLOW and the 3D groundwater solute transport model MT3DMS. The new package can simulate, in addition to water flow in the vadose zone, also solute transport involving many biogeochemical processes and reactions, including first-order degradation, volatilization, linear or nonlinear sorption, one-site kinetic sorption, two-site sorption, and two-kinetic sites sorption. Due to complex interactions at the groundwater table, certain modifications of the pressure head (compared to the original coupling) and solute concentration profiles were incorporated into the modified HYDRUS package. The performance of the newly developed model is evaluated using HYDRUS (2D/3D), and the results indicate that the new model is effective in simulating the movement of water and contaminants in the saturated-unsaturated flow domains.     

Comparing Natural Source Zone Depletion Pathways at a Fuel Release Site

Natural source zone depletion (NSZD) refers to processes within chemically impacted vadose and saturated zones that reduce the mass of contaminants remaining in a defined source control volume. Studies of large petroleum hydrocarbon release sites have shown that the depletion rate by vapor phase migration of degradation products from the source control volume through the vadose zone (V‐NSZD) is often considerably higher than the rate of depletion from the source control volume by groundwater flow carrying dissolved petroleum hydrocarbons arising from dissolution, desorption, or back diffusion, and degradation products arising from biodegradation (GW‐NSZD). In this study, we quantified vadose zone and GW‐NSZD at a small unpaved fuel release site in California typical of those in settings with predominantly low permeability media. We estimated vadose zone using a dense network of efflux monitoring locations at four sampling events over 2 years, and GW‐NSZD using groundwater monitoring data downgradient of the source control volume in three depth intervals spanning up to 9 years. On average, vadose zone was 17 times greater than GW‐NSZD during the time interval of comparison, and vadose zone was in the range of rates quantified at other sites with petroleum hydrocarbon releases. Estimating vadose zone and GW‐NSZD rates is challenging but the vadose zone rate is the best indicator of overall source mass depletion, whereas GW‐NSZD rates may be useful as baselines to quantify progress of natural or engineered remediation in portions of the saturated zone in which there are impediments to loss of methane and other gases to the vadose zone.     

Characteristics of distribution and transport of petroleum contaminants in fracture-karst water in Zibo Area, Shandong Province, China

Fracture-karst water is an important water resource for the water supply in North China. Petroleum contamination is one of the most problematic types of the groundwater pollution. The characteristics of distribution and transport of the petroleum contaminants in fracture-karst water are different from those in porous water. The flow velocity of fracture-karst water is much faster than the velocity of porous water on an average. Therefore, contaminant transport in fracture-karst water is an absolute advection-dominated problem. The plume of the petroleum contamination may extend to several kilometers from pollution sources. It was not caused by the oil pool floating on the water table but by the oil components dissolved and scattered in groundwater. The distribution of the petroleum contaminants over space are concentrated in the strong conductive zone on the plane. On the vertical section the highest concentration of the oil contaminants appeared in the strata where the contamination sources were located. The concentrations of the oil contaminants in wells changed greatly over time. Therefore, the curves of concentration versus time fluctuated greatly. The reasons are as follows. (a) Fracture-karst water has a very great velocity. (b) Local flow fields which were caused by pumping and stoppage in some wells changed frequently. (c) In fracture-karst aquifer the transport channels are complicated. (d) Residual oil in vadose zone was leached after rainfall. It is of great practical value for the control and remediation of petroleum contamination in fracture-karst aquifer to understand those characteristics.     

Vadose zone modeling of dispersed waste sites in the framework of an integrated stochastic environmental transport and impacts assessment code for the Hanford Site

The system assessment capability (SAC) is the first total-system stochastic simulator to address inventory distribution, environmental release and transport, and impacts to human health and ecological, economic, and cultural resources from hundreds of radiological and chemical waste disposal sites for the entire Hanford Site in southeast Washington State. Flow and contaminant transport modeling in the vadose zone at 720 individual sites has been integrated into the SAC stochastic software framework using the STOMP code, providing the means to define release to the regional aquifer to support the SAC groundwater transport model. Important features, events, and processes including remedial actions, time-variant natural infiltration rates, and high volume aqueous-phase discharges were addressed in the software and data. A separate data extraction program, VZGRAB, was developed to enable analysts to aggregate vadose zone release data across the hundreds of waste sites in various ways following a SAC simulation to develop an improved understanding of the system performance and uncertainty aspects.     

The New Potential for Understanding Groundwater Contaminant Transport

The groundwater remediation field has been changing constantly since it first emerged in the 1970s. The remediation field has evolved from a dissolved‐phase centric conceptual model to a DNAPL‐dominated one, which is now being questioned due to a renewed appreciation of matrix diffusion effects on remediation. Detailed observations about contaminant transport have emerged from the remediation field, and challenge the validity of one of the mainstays of the groundwater solute transport modeling world: the concept of mechanical dispersion (Payne et al. 2008). We review and discuss how a new conceptual model of contaminant transport based on diffusion (the usurper) may topple the well‐established position of mechanical dispersion (the status quo) that is commonly used in almost every groundwater contaminant transport model, and evaluate the status of existing models and modeling studies that were conducted using advection‐dispersion models.