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.     

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.     

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.     

A Three-Dimensional Analytical Model to Aid in Selecting Monitoring Locations in the Vadose Zone

Monitoring of the vadose zone is a potentially complex, time-consuming, and expensive problem. The location of monitoring points and selection of monitoring instruments can be optimized by using computer models. Numerical models developed for this purpose in the past have often been expensive and difficult to use. This paper describes a fast, three-dimensional, approximate analytical solution to the moisture content in the unsaturated zone. An analytical solution is available for steady-state drainage, whereas an approximate analytical solution is available for the transient case. The model will handle an arbitrary distribution of fluid sources, as well as vertical and horizontal impermeable boundaries.
The model may be applied to predict the incursion of fluid from accidental leakage or infiltration over large areas from unlined ponds and land treatment sites. The model is quite useful as an aid in designing monitoring or premonitoring programs near hazardous waste sites. Examples are presented to demonstrate the model's utility in estimating the maximum spread of a contaminant, the extent to which the fluid may spread with depth, the regions of high and low capillary pressure, and the non-linear behavior of the saturation when drainage from several sources in considered. These results are useful for the placement of monitoring locations and the selection of appropriate instruments, and as a tool in working with regulatory agencies to design monitoring programs. A glimpse of the future is necessary for today's planning. Computer models are some of the most useful crystal balls we have available.     

Limitations of Current Approaches for Predicting Groundwater Vulnerability from PFAS Contamination in the Vadose Zone

Published literature for reported sorption coefficients (K_d) of eight anionic per- and polyfluoroalkyl substances (PFAS) in soil was reviewed. K_d values spanned three to five log units indicating that no single value would be appropriate for use in estimating PFAS impacts to groundwater using existing soil-water partition equations. Regression analysis was used to determine if the soil or solution parameters might be used to predict K_d values. None of the 15 experimental parameters collected could individually explain variability in reported K_d values. Significant associations between K_d and soil calcium and sodium content were found for many of the selected PFAS, suggesting that soil cation content may be critical to PFAS sorption, as previously noted in sources like Higgins and Luthy (2006), while organic carbon content was significant only at elevated levels (>5%). Unexplained discrepancies between the results from studies where PFAS were introduced to soil and desorbed in the laboratory and those that used material from PFAS-impacted sites suggest that laboratory experiments may be overlooking some aspects critical to PFAS sorption. Future studies would benefit from the development and use of standardized analytical methods to improve data quality and the establishment of soil parameters appropriate for collection to produce more complete data sets for predictive analysis.     

A New Modification to the Chemical Mass Balance Receptor Model for Volatile Organic Compound Source Apportionment

In this study, a modification to the chemical mass balance (CMB) receptor model presented in an earlier work was expanded to account for the changes in volatile organic compound (VOC) source fingerprints due to atmospheric reactions of VOCs that take place after being emitted to the atmosphere. The photochemical reactions consume VOCs that participate in, causing changes in the source fingerprints. These changes are of considerable magnitude when the travel durations from the source to the receptor (measurement point) are considered. The current study focuses on expansion of the integrated reaction rates of VOCs with ambient reactive species such as OH ^? , O₃, NO₃, and O ^? in order to estimate the source emission profiles simultaneously at the receptor site. Two test cases with different travel times and with different ambient OH ^? , O₃, and NO₃ concentrations were also provided to compare the standard model, the modified model suggested in the previous work, and the current modification. F‐tests were also performed to determine whether the changes in source compositions are significant or not. The results from both the standard model and the modified model were evaluated in terms of χ², R², percent mass apportioned (MA), and a best fit (BF) measure. Maximum values of BF for the test cases from the three models were 0.70 ± 0.03, 0.74 ± 0.05, and 1.000 ± 0.00, respectively, indicating that the current modification increases the performance of two previous models and was better in explaining the effects of chemical reactions of VOCs.     

Effect of NAPL Source Morphology on Mass Transfer in the Vadose Zone

The generation of vapor‐phase contaminant plumes within the vadose zone is of interest for contaminated site management. Therefore, it is important to understand vapor sources such as non‐aqueous‐phase liquids (NAPLs) and processes that govern their volatilization. The distribution of NAPL, gas, and water phases within a source zone is expected to influence the rate of volatilization. However, the effect of this distribution morphology on volatilization has not been thoroughly quantified. Because field quantification of NAPL volatilization is often infeasible, a controlled laboratory experiment was conducted in a two‐dimensional tank (28 cm × 15.5 cm × 2.5 cm) with water‐wet sandy media and an emplaced trichloroethylene (TCE) source. The source was emplaced in two configurations to represent morphologies encountered in field settings: (1) NAPL pools directly exposed to the air phase and (2) NAPLs trapped in water‐saturated zones that were occluded from the air phase. Airflow was passed through the tank and effluent concentrations of TCE were quantified. Models were used to analyze results, which indicated that mass transfer from directly exposed NAPL was fast and controlled by advective‐dispersive‐diffusive transport in the gas phase. However, sources occluded by pore water showed strong rate limitations and slower effective mass transfer. This difference is explained by diffusional resistance within the aqueous phase. Results demonstrate that vapor generation rates from a NAPL source will be influenced by the soil water content distribution within the source. The implications of the NAPL morphology on volatilization in the context of a dynamic water table or climate are discussed.     

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.     

Influence of Fluctuating Groundwater Table on Volatile Organic Chemical Emission Flux at a Dissolved Chlorinated-Solvent Plume Site

Groundwater elevation fluctuation has been recognized as one mechanism causing temporal indoor air volatile organic chemical (VOC) impacts in vapor intrusion risk assessment guidance. For dissolved VOC sources, groundwater table fluctuation shortens/lengthens the transport pathway, and delivers dissolved contaminants to soils that are alternating between water saturated and variably saturated conditions, thereby enhancing volatilization potential. To date, this mechanism has not been assessed with field data, but enhanced VOC emission flux has been observed in lab-scale and modeling studies. This work evaluates the impact of groundwater elevation changes on VOC emission flux from a dissolved VOC plume into a house, supplemented with modeling results for cyclic groundwater elevation changes. Indoor air concentrations, air exchange rates, and depth to groundwater (DTW) were collected at the study house during an 86-d constant building underpressurization test. These data were used to calculate changes in trichloroethylene (TCE) emission flux to indoor air, during a period when DTW varied daily and seasonally from about 3.1 to 3.4 m below the building foundation (BF). Overall, TCE flux to indoor air varied by about 50% of the average, without any clear correlation to changes in DTW or its change rate. To complement the field study, TCE surface emission fluxes were simulated using a one-dimensional model (HYDRUS 1D) for conditions similar to the field site. Simulation results showed time-averaged surface TCE fluxes for cyclic water-table elevations were greater than for stationary water-table conditions at an equivalent time-averaged water-table position. The magnitudes of temporal TCE emission flux changes were generally less than 50% of the time-averaged flux, consistent with the field site observations. Simulation results also suggested that TCE emission flux changes due to groundwater fluctuation are likely to be significant at sites with shallow groundwater (e.g., < 0.5 m BF) and permeable soil types (e.g., sand).     

Influence of Shallow Geology on Volatile Organic Chemical Attenuation from Groundwater to Deep Soil Gas

Vapor intrusion pathway evaluations commonly begin with a comparison of volatile organic chemical (VOC) concentrations in groundwater to generic, or Tier 1, screening levels. These screening levels are typically quite low reflecting both a desired level of conservatism in a generic risk screening process as well as limitations in understanding of physical and chemical processes that impact vapor migration in the subsurface. To study the latter issue, we have collected detailed soil gas and groundwater vertical concentration profiles and evaluated soil characteristics at seven different sites overlying chlorinated solvent contaminant plumes. The goal of the study was to evaluate soil characteristics and their impacts on VOC attenuation from groundwater to deep soil gas (i.e., soil gas in the unsaturated zone within 2 feet of the water table). The study results suggest that generic screening levels can be adjusted by a factor of 100× at sites with fine‐grained soils above the water table, as identified by visual observations or soil air permeability measurements. For these fine‐grained soil sites, the upward‐adjusted screening levels maintain a level of conservatism while potentially eliminating the need for vapor intrusion investigations at sites that may not meet generic screening criteria.     

Passive Samplers for Monitoring VOCs in Groundwater and the Prospects Related to Mass Flux Measurements

Measurement and interpretation of mass fluxes in favor of concentrations is gaining more and more interest, especially within the framework of the characterization and management of large-scale volatile organic carbon (VOC) groundwater contamination (source zones and plumes). Traditional methods of estimating contaminant fluxes and discharges involve individual measurements/calculations of the Darcy water flux and the contaminant concentrations. However, taken into account the spatially and temporally varying hydrologic conditions in complex, heterogeneous aquifers, higher uncertainty arises from such indirect estimation of contaminant fluxes. Therefore, the potential use of passive sampling devices for the direct measurement of groundwater-related VOC mass fluxes is examined. A review of current passive samplers for the measurement of organic contaminants in water yielded the selection of 18 samplers that were screened for a number of criteria. These criteria are related to the possible application of the sampler for the measurement of VOC mass fluxes in groundwater. This screening study indicates that direct measurement of VOC mass fluxes in groundwater is possible with very few passive samplers. Currently, the passive flux meter (PFM) is the only passive sampler which has proven to effectively measure mass fluxes in near source groundwater. A passive sampler for mass flux measurement in plume zones with regard to long-term monitoring (several months to a year) still needs to be developed or optimized. A passive sampler for long-term monitoring of contaminant mass fluxes in groundwater would be of considerable value in the development of risk-based assessment and management of soil and groundwater pollutions.     

Screening of Emerging Volatile Organic Contaminants in Shallow Groundwater in East China

In order to collect baseline information on the environmental occurrence of volatile organic compounds (VOCs) in groundwater in East China, shallow groundwater samples were collected from five alluvial plains in East China in 2008 to 2009. All samples were analyzed for 54 VOCs representing a wide variety of uses and origins. Sampling sites were mainly selected in the areas to be susceptible to contamination from human activities in terms of previous hydrogeological survey. The data of all samples showed a variety of different hydrogeological systems with potential sources of VOCs, with 36 of the 54 VOCs being found. The most frequently detected compounds include naphthalene (56.9%), chloroform (16.9%), 1,2‐dichloroethane (16.2%), 1,2‐dichloropropane (13.1%), and 1,2,3‐trichlorobenzene (12.3%). The concentrations of methylene chloride, 1,2‐dichloroethane, carbon tetrachloride, trichloroethene, 1,2‐dichloropropane, and tetrachloroethene exceeded the relating drinking water standards. Future work will be needed to identify those factors that are most important in determining the occurrence and concentrations of VOCs in groundwater in China.     

On Evaluating Characteristics of the Solute Transport in the Arid Vadose Zone

The transport of bromide (Br) under matric heads of 0, ?2, ?5, and ?10 cm using undisturbed soil columns was investigated for understanding the solute transport in arid soils. Undisturbed soil cores were collected at ground surface, directly below where tension infiltrometer measurements were made in the Amargosa Desert, Nevada, United States. Laboratory experiments were conducted by introducing water containing Br tracer into a soil column maintained at steady‐state conditions. The observed data of breakthrough curves (BTC) were well fitted to an one‐region model, except for the cores at saturation, and a core at the matric head of ?5 cm, from which the observed data were better fitted to a two‐region model. Fitted pore water velocities with the one‐region model ranged from 1.2 to 56.6 cm/h, and fitted dispersion coefficients (D) ranged from 2.2 to 100 cm²/h. Results for the core analyzed with the two‐region model indicated that D ranged from 27.6 to 70.9 cm²/h at saturation, and 25.7 cm²/h at the matric head of ?5 cm; fraction of mobile water (β) ranged from 0.18 to 0.65, and mass transfer coefficient (ω) ranged from 0.006 to 0.03. In summary, the water fluxes and Br dispersion coefficients at investigated matric heads were very high due to the coarseness of the soils and possibly due to preferential flow pathways. These high water fluxes and Br dispersion coefficients would lead to a higher risk of deeper leaching accumulating nitrate nitrogen to the groundwater, and have significant effects on the desert ecosystem.     

Groundwater Sampling at ISCO Sites: Binary Mixtures of Volatile Organic Compounds and Persulfate

In situ chemical oxidation involves the introduction of a chemical oxidant into the subsurface for the purpose of transforming groundwater contaminants into harmless by‐products. Owing to oxidant persistence, groundwater samples collected at hazardous waste sites may contain both the contaminant(s) and the oxidant in a “binary mixture.” Binary mixtures composed of sodium persulfate (2.5 g/L; 10.5 mM) and volatile organic compounds (VOCs) (benzene, toluene, m‐xylene, perchloroethylene, trichloroethylene) were analyzed to assess the impact on the quality of the sample. A significant decline (49 to 100%) in VOC concentrations was measured in binary mixtures using gas chromatography (GC) purge and trap, and GC mass spectroscopy headspace methods. Preservation of the binary mixture samples was achieved through the addition of ascorbic acid (99 to 100% VOC average recovery). High concentrations of ascorbic acid (42 to 420 mM) did not interfere in the measurement of the VOCs and did not negatively impact the analytical instruments. High concentrations of ascorbic acid favored the reaction between persulfate and ascorbic acid while limiting the reaction between persulfate and VOCs. If an oxidant is detected and the binary sample is not appropriately preserved, the quality of the sample is likely to be compromised.     

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.     

Numerical Investigation of the Impact of Ethanol on Flow in the Vadose Zone

There is a need to elucidate the impact of ethanol on the subsurface environment because of the application of ethanol as automotive fuel. This study quantifies the effects of changes in surface tension, viscosity, and density induced by ethanol on the transmission and retention of water in the vadose zone. The HYDRUS‐1D model was modified to simulate two different scenarios of flow in a sandy loam involving ponding (constant head) or spillage with a subsequent rainfall event (constant flux). Solutions containing different amounts of the highly miscible ethanol (10, 50, and 100% by weight) as well as pristine water were considered. During ponding, ethanol reduced the amount of fluid entering the soil and slowed down the advancement of the wetting front. Viscosity effects were predominant for this scenario, reducing the average depth of the infiltrating liquid up to 44%. The total amount of pure ethanol that entered the soil was 11.38 vs. 17.64 cm for pure water. For the spillage scenario, the results suggest that density has little impact on the liquid movement. Surface tension effects are predominant in the upper portion of the soil. The changes in hydraulic conductivity due to ethanol‐induced modifications of solution viscosity are responsible for the slower advancement of the moisture front. The 10% ethanol solution moved 43.1% faster than pure ethanol during the first 2 d because of viscosity and surface tension effects.     

Presence of Semi‐Volatile Organic Contaminants in Shallow Groundwater of Selected Regions in China

A pioneering investigation of semi‐volatile organic compounds (SVOCs) in shallow groundwater in China was hereby reported. Representative groundwater samples were collected from three selected regions: Eastern Hai River Plain, Yangtze River Delta, and Yunnan‐Guizhou Plateau, and analyzed for 103 SVOCs linked to agricultural and industrial practices. Analytical results showed that 70 of the 103 SVOCs were present in the groundwater samples, a detection frequency of approximately 86%. Compounds detected most frequently included P,P′‐DDT (53.49%, MDL 0.0007 µg/L), 2,4‐dinitrotoluene (51.16%, MDL 0.02 µg/L), and phenol (51.16%, MDL 0.02 µg/L). Fifteen SVOCs, such as P,P′‐DDT, 2,4‐dinitrotoluene, heptachlor, and aldrin, were detected at concentrations exceeding the USA National Recommended Water Quality Criteria‐2009 (USNRWQC‐2009). Most of these 15 SVOCs belong to polycyclic aromatic hydrocarbons and organochlorine pesticides. The detection of SVOCs in the Yunnan‐Guizhou Plateau warrants special concern, since this region has limited human activities and been assumed as an environmentally pristine area. The data from this work are expected to contribute to the database of contemporary groundwater quality in China.