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.     

Sewer Gas: An Indoor Air Source of PCE to Consider During Vapor Intrusion Investigations

The United States Environmental Protection Agency (USEPA) is finalizing its vapor intrusion guidelines. One of the important issues related to vapor intrusion is background concentrations of volatile organic compounds (VOCs) in indoor air, typically attributed to consumer products and building materials. Background concentrations can exist even in the absence of vapor intrusion and are an important consideration when conducting site assessments. In addition, the development of accurate conceptual models that depict pathways for vapor entry into buildings is important during vapor intrusion site assessments. Sewer gas, either as a contributor to background concentrations or as part of the site conceptual model, is not routinely evaluated during vapor intrusion site assessments. The research described herein identifies an instance where vapors emanating directly from a sanitary sewer pipe within a residence were determined to be a source of tetrachloroethylene (PCE) detected in indoor air. Concentrations of PCE in the bathroom range from 2.1 to 190 µg/m³ and exceed typical indoor air concentrations by orders of magnitude resulting in human health risk classified as an “Imminent Hazard” condition. The results suggest that infiltration of sewer gas resulted in PCE concentrations in indoor air that were nearly two orders of magnitude higher as compared to when infiltration of sewer gas was not known to be occurring. This previously understudied pathway whereby sewers serve as sources of PCE (and potentially other VOC) vapors is highlighted. Implications for vapor intrusion investigations are also discussed.     

Evaluation of the Johnson and Ettinger Model for Prediction of Indoor Air Quality

Screening level models are now commonly used to estimate vapor intrusion for subsurface volatile organic compounds (VOCs). Significant uncertainty is associated with processes and models and, to date, there has been only limited field-based evaluation of models for this pathway. To address these limitations, a comprehensive evaluation of the Johnson and Ettinger (J&E) model is provided through sensitivity analysis, comparisons of model-predicted to measured vapor intrusion for 11 petroleum hydrocarbon and chlorinated solvent sites, and review of radon and flux chamber studies. Significant intrusion was measured at five of 12 sites with measured vapor attenuation ratios (α_m's) (indoor air/source vapor) ranging from ∼1 × 10⁻⁶ to 1 × 10⁻⁴. Higher attenuation ratios were measured for studies using radon, inert tracers, and flux chambers; however, these ratios are conservative owing to boundary conditions and tracer properties that are different than those at most VOC-contaminated sites. Reasonable predictions were obtained using the J&E model with comparisons indicating that model-predicted vapor attenuation ratios (α_p's) were on the same order, or less than the α_m's. For several sites, the (m were approximately two orders of magnitude less than the a 's indicating that the J&E model is conservative in these cases. The model comparisons highlight the importance in using appropriate input parameters for the J&E model. The regulatory implications associated with use of the J&E model to derive screening criteria are also discussed.     

Modeling Fate and Transport of Volatile Organic Compounds (VOCs) Inside Sewer Systems

Hazardous waste site investigations have shown that volatile organic compounds (VOCs) can be transported via sewer pipes and migrate into indoor spaces. Despite field data confirming the presence of this exposure pathway, there is lack of context-based numerical models that provide guidance to characterize and predict VOCs concentration in sewer gas at vapor intrusion sites. Particularly, this poses a challenge when assessing and mitigating risks associated with these exposure pathways. Therefore, a numerical model has been developed to simulate the concentration of VOCs in sewer gas in different stages throughout the sewer lines. The developed model considers various input parameters, including temperature, sewer liquid depth, groundwater depth, and sewer construction characteristics to incorporate local and operational conditions. The model's output is verified using field data from a sewer system constructed near a Superfund site. Moreover, a sensitivity analysis was conducted to evaluate the model's response to variation of the external input parameters. To the best of our knowledge, this study is the first attempt to model VOCs concentration in sewer gas, particularly to address vapor intrusion. The developed model can be used as a numerical tool to support the development of sewer assessment guidelines, risk assessment studies, and mitigation strategies.     

Sea‐cliff retreat and shore platform widening: steady‐state equilibrium?

We challenge the notion of steady‐state equilibrium in the context of progressive cliff retreat on micro‐tidal coasts. Ocean waves break at or close to the abrupt seaward edge of near‐horizontal shore platforms and then rapidly lose height due to turbulence and friction. Conceptual models assume that wave height decays exponentially with distance from the platform edge, and that the platform edge does not erode under stable sea‐level. These assumptions combine to a steady‐state view of Holocene cliff retreat. We argue that this model is not generally applicable. Recent data show that: (1) exponential decay in wave height is not the most appropriate conceptual model of wave decay; (2) by solely considering wave energy at gravity wave frequencies the steady‐state model neglects a possible formative role for infragravity waves. Here we draw attention to possible mechanisms through which infragravity waves may drive cliff retreat over much greater distances (and longer timescales) than imaginable under the established conceptual model. Copyright © 2013 John Wiley & Sons, Ltd.     

Interstitial transport of solutes in non-steady state accumulating and compacting sediments

A general one-dimensional equation for interstitial transport in accumulating and compacting sediments under non-steady state conditions is derived. As a consequence of compaction the metric along the path of a given horizon, i.e. the spatial distance between neighbouring particles, changes continually. Special emphasis is put on the treatment of advection caused by compaction. The resulting partial differential equation for the interstitial concentration of a given solute contains terms which can be evaluated based on data from a single sediment core. In addition, an integral over the time-derivative of porosity appears which would make it necessary to compare cores from the same site but at different times. Under quite general assumptions this last term may, however, be transformed into a form for which evaluation from a single core becomes possible. Several special solutions are treated such as total steady state, steady state at the surface, non-constant sedimentation rate with steady state compaction, and non-steady state with steady state compaction. The last case applies, e.g., to diffusion under the influence of changing boundary conditions at the water/sediment interface while the accumulation process remains in steady state.     

Analytical Solutions for Steady-State Gas Flow in Layered Soils with Field Applications

Soil vapor extraction (SVE) is widely used to remove volatile organic compounds from the vadose zone. Design of SVE systems rely largely upon vacuum responses and limited vapor concentration data measured during short-term soil gas extraction tests performed in single extraction wells. Interpretation of such vacuum data is often simply a rule of thumb as most field sites have layering complexity negating applicability of existing analytical models. This paper provides the derivation of an analytical model for steady, axisymmetric gas flow in heterogeneous (layered) soils from a single well. A general, variable flow boundary condition along the well screen represents actual conditions more closely than a uniform flow or uniform well pressure condition. Each soil layer is assumed homogeneous with anisotropic gas permeability. The solution is derived using the generalized integral transform technique and includes expressions for vacuum, velocities, and streamlines. The model is applied to the interpretation of multiple well tests at a field site and uses linear superposition to extend the flow model to multi-well extraction. The demonstration site included an array of vacuum monitoring data collected during nine individual well flow tests. A method of normalizing the vacuum data is illustrated that allowed the full data set to be employed in a single calibration effort. The test site also included a surface cap with an apparent vertical permeability two to three orders of magnitude smaller than the sands of the vadose zone. This large permeability contrast posed no difficulties in evaluating the solution.     

A New Analytical Treatment of Airflow to Inlet Wells in Soil Vapor Extraction Systems

This paper provides a new analytical model of airflow to inlet wells in soil vapor extraction systems. It is based on a recent analytical solution of airflow to a single vapor extraction well by Bahr and Joss (1995), which updated the previous model of Baehr and Hult (1991). Baehr and Joss (1995) treated the air leakage through the surface as an air flux boundary condition, whereas Baehr and Hult (1991) approximated the leakage as a distributed source imposed in the governing airflow equation. The new analytical model shows significant improvement on air-flow assessment over the previous model by Ge and Liao (1996), which could underestimate the efficiency of airflow to inlet wells by as much as 27% in a typical vapor extraction system.     

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

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

新疆于田Ms7.3地震前重力场变化的质源体特征

应用中国地壳运动观测网络工程获得的1998-2005年4期重力场变化观测资料,结合EGM2008的重力场模型作为区域背景场.对2008年新疆于田Ms7.3地震前的重力场变化特征进行深入分析,通过位场延拓和空间求导等方法,对震前的质源体边界特征进行跟踪和估定.同时,尝试利用一种应用空间相关性加权分析方法给出地震危险性空间...     

The identifiability of parameters in a water quality model of the Biebrza River, Poland

The identifiability of model parameters of a steady state water quality model of the Biebrza River and the resulting variation in model results was examined by applying the Monte Carlo method which combines calibration, identifiability analysis, uncertainty analysis, and sensitivity analysis. The water quality model simulates the steady state concentration profiles of chloride, phosphate, ammonium, and nitrate as a function of distance along a river. The water quality model with the best combination of parameter values simulates the observed concentrations very well. However, the range of possible modelled concentrations obtained for other more or less equally eligible combinations of parameter values is rather wide. This range in model outcomes reflects possible errors in the model parameters. Discrepancies between the range in model outcomes and the validation data set are only caused by errors in model structure, or (measurement) errors in boundary conditions or input variables. In this sense the validation procedure is a test of model capability, where the effects of calibration errors are filtered out. It is concluded that, despite some slight deviations between model outcome and observations, the model is successful in simulating the spatial pattern of nutrient concentrations in the Biebrza River.     

Utility of Compound‐Specific Isotope Analysis for Vapor Intrusion Investigations

Different types of data can be collected to evaluate whether or not vapor intrusion is a concern at sites impacted with volatile organic compound (VOC) contamination in the subsurface. Typically, groundwater, soil gas, or indoor air samples are collected to determine VOC concentrations in the different media. Sample results are evaluated using a “multiple lines of evidence” approach to interpret whether vapor intrusion is occurring. Data interpretation is often not straightforward because of many complicating factors, particularly in the evaluation of indoor air. More often than not, indoor air sample results are affected by indoor or other background sources making interpretation of concentration‐based data difficult using conventional sampling approaches. In this study, we explored the practicality of compound‐specific isotope analysis (CSIA) as an additional type of evidence to distinguish between indoor sources and subsurface sources (i.e., vapor intrusion). We developed a guide for decision‐making to facilitate data interpretation and applied the guidelines at four different test buildings. To evaluate the effectiveness of the CSIA method for vapor intrusion applications, we compared the interpretation from CSIA to interpretations based on data from two different investigation approaches: conventional sampling and on‐site GC/MS analysis. Interpretations using CSIA were found to be generally consistent with the other approaches. In one case, CSIA provided the strongest line of evidence that vapor intrusion was not occurring and that a VOC source located inside the building was the source of VOCs in indoor air.     

Acquisition design for direct reflectivity and velocity estimation from blended and irregularly sampled data

Blended acquisition along with efficient spatial sampling is capable of providing high-quality seismic data in a cost-effective and productive manner. While deblending and data reconstruction conventionally accompany this way of data acquisition, the recorded data can be processed directly to estimate subsurface properties. We establish a workflow to design survey parameters that account for the source blending as well as the spatial sampling of sources and detectors. The proposed method involves an iterative scheme to derive the survey design leading to optimum reflectivity and velocity estimation via joint migration inversion. In the workflow, we extend the standard implementation of joint migration inversion to cope with the data acquired in a blended fashion along with irregular detector and source geometries. This makes a direct estimation of reflectivity and velocity models feasible without the need of deblending or data reconstruction. During the iterations, the errors in reflectivity and velocity estimates are used to update the survey parameters by integrating a genetic algorithm and a convolutional neural network. Bio-inspired operators enable the simultaneous update of the blending and sampling operators. To relate the choice of survey parameters to the performance of joint migration inversion, we utilize a convolutional neural network. The applied network architecture discards suboptimal solutions among newly generated ones. Conversely, it carries optimal ones to the subsequent step, which improves the efficiency of the proposed approach. The resultant acquisition scenario yields a notable enhancement in both reflectivity and velocity estimation attributable to the choice of survey parameters.     

Simulated Soil Vapor Intrusion Attenuation Factors Including Biodegradation for Petroleum Hydrocarbons

Aerobic biodegradation can contribute significantly to the attenuation of petroleum hydrocarbons vapors in the unsaturated zone; however, most regulatory guidance for assessing potential human health risks via vapor intrusion to indoor air either neglect biodegradation in developing generic screening levels or allow for only one order of magnitude additional attenuation for aerobically degradable compounds, which may be overly conservative in some cases. This paper describes results from three-dimensional numerical model simulations of vapor intrusion for petroleum hydrocarbons to assess the influence of aerobic biodegradation on the attenuation factor for a variety of source concentrations and depths for residential buildings with basements and slab-on-grade construction. The simulations conducted in this study provide a framework for understanding the degree to which bioattenuation will occur under a variety of scenarios and provide insight into site conditions that will result in significant biodegradation. This improved understanding may be used to improve the conceptual model of contaminant transport, guide field data collection and interpretation, and estimate semi-site-specific attenuation factors for combinations of source concentrations, source depth, oxygen distribution, and building characteristics where site conditions reasonably match the scenarios simulated herein.     

UXO target area identification with hidden Markov models

Site characterization activities at potential unexploded ordnance (UXO) sites rely on sparse sampling collected as geophysical surveys along strip transects. From these samples, the locations of target areas, those regions on the site where the geophysical anomaly density is significantly above the background density, must be identified. A target area detection approach using a hidden Markov model (HMM) is developed here. HMM’s use stationary transition probabilities from one state to another for steps between adjacent locations as well as the probability of any particular observation occurring given each possible underlying state. The approach developed here identifies the transition probabilities directly from the conceptual site model (CSM) created as part of the UXO site characterization process. A series of simulations examine the ability of the HMM approach to simultaneously determine the target area locations within each transect and to estimate the unknown anomaly intensity within the identified target area. The HMM results are compared to those obtained using a simpler target detection approach that considers the background anomaly density to be defined by a Poisson distribution and each location to be independent of any adjacent location. Results show that the HMM approach is capable of accurately identifying the target locations with limited false positive identifications when both the background and target are intensities are known. The HMM approach is relatively robust to changes in the initial estimate of the target anomaly intensity and is capable of identifying target locations and the corresponding target anomaly intensity when this intensity is approximately 60% higher than the background intensity at intensities that are representative of actual field sites. Application to data collected from a wide area assessment field site show that the HMM approach identifies the area of the site with elevated anomaly intensity with few false positives. This field site application also shows that the HMM results are relatively robust to changes in the transect width.     

Groundwater monitoring strategies for variable contaminant migration boundaries

Abstract

Detection efficiencies of alternative groundwater monitoring networks were evaluated in relation to distance to a buffer zone (contaminant migration) boundary. This boundary establishes a distance limit within which contaminant plumes should pass through monitoring wells, located on curvilinear segments (monitoring loci) near a waste storage facility. Alternative strategies allocated monitoring wells to loci at specified distances, measured parallel to groundwater flow, from the downgradient boundaries of a landfill. One approach constrained wells to equal spacing, measured perpendicular to groundwater flow. Compressing well locations 10% closer to the downgradient corner of the landfill rendered alternative monitoring configurations. Computations by a monitoring efficiency model indicated: (a) networks largely maintained detection efficiency for different contaminant migration boundaries; (b) one network most efficiently attained a target detection capability for all contaminant migration boundaries; and (c) compressed networks slightly outperformed equal-spaced counterparts. Compressed networks with more wells along closer monitoring loci best maintained the detection efficiency when shifting the contaminant migration boundary closer to the landfill. Procedures described in this paper may be useful for examining trade-offs between monitoring efficiency and distance limits of contaminant travel at landfills posing potential hazards to underlying groundwater.     

A comprehensive physical pattern of land-air dynamic and thermal structure on the Qinghai-Xizang Plateau

According to the boundary layer observations of three stations (Garze, Damxung and Qamdu) and relevant earth satellite, radiosonde and surface observations during the intensive observational period (IOP) of the second Tibetan (Qinghai-Xizang) Plateau Experiment of atmospheric science (TIPEX), the land-air physical process and dynamic model on the Tibetan Plateau were comprehensively analyzed in this study. The dynamic characteristics of boundary layer and the rules of turbulent motion on the plateau were illustrated. The characteristics of distributions of wind speed and direction with mutiple-layer structure and deep convective mixed layer on the plateau, the strong buoyancy effect in turbulent motion on the plateau on which the air density is obviously smaller than on the plain, and the Ekman spiral and its dynamic pump effect of the plateau deep boundary layer have been found. The local static distribution of water vapor and the horizontal advection of water vapor in the plateau boundary layer were studied. The abnomal thermodynamic structure on the plateau surface and boundary layer, including the plateau strong radiation phenomenon and strong heating source characteristics of the middle plateau, was also analyzed. The authors synthesized the above dynamic and thermodynamic structures of both surface and boundary layers on the plateau and posed the comprehensive physical model of the turbulence and convective mixture mechanism on the plateau boundary layer. The characteristics of formation, development and movement for convective cloud cluster over the plateau influencing floods in the Yangtze River area of China were studied. The conceptual model of dynamic and thermodynamic structures of turbulent motion and convective plume related to the frequent occurrence of "pop-corn-like" cloud system is given as well.     

Parameter estimation in nonlinear environmental problems

Popular parameter estimation methods, including least squares, maximum likelihood, and maximum a posteriori (MAP), solve an optimization problem to obtain a central value (or best estimate) followed by an approximate evaluation of the spread (or covariance matrix). A different approach is the Monte Carlo (MC) method, and particularly Markov chain Monte Carlo (MCMC) methods, which allow sampling from the posterior distribution of the parameters. Though available for years, MC methods have only recently drawn wide attention as practical ways for solving challenging high-dimensional parameter estimation problems. They have a broader scope of applications than conventional methods and can be used to derive the full posterior pdf but can be computationally very intensive. This paper compares a number of different methods and presents improvements using as case study a nonlinear DNAPL source dissolution and solute transport model. This depth-integrated semi-analytical model approximates dissolution from the DNAPL source zone using nonlinear empirical equations with partially known parameters. It then calculates the DNAPL plume concentration in the aquifer by solving the advection-dispersion equation with a flux boundary. The comparison is among the classical MAP and some versions of computer-intensive Monte Carlo methods, including the Metropolis–Hastings (MH) method and the adaptive direction sampling (ADS) method.     

Simulation of the Vapor Intrusion Process for Nonhomogeneous Soils Using a Three-Dimensional Numerical Model

This paper presents model simulation results of vapor intrusion into structures built atop sites contaminated with volatile or semivolatile chemicals of concern. A three-dimensional finite element model was used to investigate the importance of factors that could influence vapor intrusion when the site is characterized by nonhomogeneous soils. Model simulations were performed to examine how soil layers of differing properties alter soil-gas concentration profiles and vapor intrusion rates into structures. The results illustrate difference in soil-gas concentration profiles and vapor intrusion rates between homogeneous and layered soils. The findings support the need for site conceptual models to adequately represent a site's geology when conducting site characterizations, interpreting field data, and assessing the risk of vapor intrusion at a given site. For instance, in layered geologies, a lower permeability and diffusivity soil layer between the source and building often limits vapor intrusion rates, even if a higher permeability layer near the foundation permits increased soil-gas flow rates into the building. In addition, the presence of water-saturated clay layers can considerably influence soil-gas concentration profiles. Therefore, interpreting field data without accounting for clay layers in the site conceptual model could result in inaccurate risk calculations. Important considerations for developing more accurate conceptual site models are discussed in light of the findings.     

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.