Spatial Variability of Soil-Gas Concentrations near and beneath a Building Overlying Shallow Petroleum Hydrocarbon–Impacted Soils

Data requirements for assessing the significance of the soil vapor intrusion pathway are evolving, and the collection and interpretation of subslab and near-slab soil-gas samples are under discussion. The potential for different assessment paradigms for aerobically biodegradable and recalcitrant chemicals is also frequently debated. In this work, the soil-gas distribution beneath and around a slab-on-grade building overlying shallow (0.5 to >1.5 m below ground surface) petroleum hydrocarbon–impacted coarse alluvial soils was studied. The study spanned about 12 months, including the sampling of soil-gas hydrocarbon and oxygen concentrations, subslab soil vs. building pressure differentials and included weather conditions. Three-dimensional soil-gas concentration "snapshots" using samples from 79 soil-gas sampling points are presented here. Significant spatial variability was observed with hydrocarbon and oxygen concentrations ranging from about <0.01 to 200 mg/L and 0 to 21% v/v, respectively. The presence of oxygen and the depth to petroleum-impacted soils appeared to be the dominant factors in controlling the soil-gas distribution; the depletion of hydrocarbons over short lateral and vertical distances (<2 m) was observed in the well-oxygenated regions. Composition data suggest preferential biodegradation of lighter compounds at some points, as reflected in the ratio of the masses of chemicals eluting on the gas chromatography between methane and pentane (C1 and C5) and all others after pentane (>C5).     

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.     

Macro- and Micro-Purge Soil-Gas Sampling Methods for the Collection of Contaminant Vapors

Purging influence on soil‐gas concentrations for volatile organic compounds (VOCs), as affected by sampling tube inner diameter and sampling depth (i.e., system volume) for temporary probes in fine‐grained soils, was evaluated at three different field sites. A macro‐purge sampling system consisted of a standard, hollow, 3.2‐cm outer diameter (OD) drive probe with a retractable sampling point attached to an appropriate length of 0.48‐cm inner diameter (ID) Teflon^® tubing. The macro‐purge sampling system had a purge system volume of 24.5 mL at a 1‐m depth. In contrast, the micro‐purge sampling systems were slightly different between the field sites and consisted of a 1.27‐cm OD drive rod with a 0.10‐cm ID stainless steel tube or a 3.2‐cm OD drive rod with a 0.0254‐cm inner diameter stainless steel tubing resulting in purge system volumes of 1.2 and 7.05 mL at 1‐m depths, respectively. At each site and location within the site, with a few exceptions, the same contaminants were identified in the same relative order of abundances indicating the sampling of the same general soil atmosphere. However, marked differences in VOC concentrations were identified between the sampling systems, with micro‐purge samples having up to 27 times greater concentrations than their corresponding macro‐purge samples. The higher concentrations are the result of a minimal disturbance of the ambient soil atmosphere during purging. The minimal soil‐gas atmospheric disturbance of the micro‐purge sampling system allowed for the collection of a sample that is more representative of the soil atmosphere surrounding the sampling point. That is, a sample that does not contain an atmosphere that has migrated from distance through the geologic material or from the surface in response to the vacuum induced during purging soil‐gas concentrations. It is thus recommended that when soil‐gas sampling is conducted using temporary probes in fine‐grained soils, the sampling system use the smallest practical ID soil‐gas tubing and minimize purge volume to obtain the soil‐gas sample with minimal risk of leakage so that proper decisions, based on more representative soil‐gas concentrations, about the site can be made.     

Rapid Assessment of Trichloroethylene in Ground Water

On-site analysis of trichloroethylene (TCE) in aqueous samples by head- space sample preparation and gas chromatography (HS/GC) provides for quick and precise concentration estimates. This analytical approach is well suited for the on-site determination of volatile organic compounds (VOCs) in a variety of sample matrices, including ground water and saturated and unsatured soils. For these reasons, HS/GC can be used to establish analyte concentrations on a near real time basis to help select appropriate casing material during monitoring well installation. This application and the collection of multiple well samples during sampling events facilitates the hydrogeological site interpretation and the formulation of remediation strategies.     

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.     

High Purge Volume Sampling—A New Paradigm for Subslab Soil Gas Monitoring

Subslab soil gas sampling and analysis is a common line of evidence for assessing human health risks associated with subsurface vapor intrusion to indoor air for volatile organic compounds; however, conventional subslab sampling methods have generated data that show substantial spatial and temporal variability, which often makes the interpretation difficult. A new method of monitoring has been developed and tested that is based on a concept of integrating samples over a large volume of soil gas extracted from beneath the floor slab of a building to provide a spatially averaged subslab concentration. Regular field screening is also conducted to assess the trend of concentration as a function of the volume removed to provide insight into the spatial distribution of vapors at progressive distances away from the point of extraction. This approach minimizes the risk of failing to identify the areas of elevated soil vapor concentrations that may exist between discrete sample locations, and can provide information covering large buildings with fewer holes drilled through the floor. The new method also involves monitoring the extraction flow rate and transient vacuum response for mathematical analysis to help interpret the vapor concentration data and to support an optimal design for any subslab venting system that may be needed.     

Soil-Gas Surveying for Subsurface Gasoline Contamination Using Total Organic Vapor Detection Instruments Part I. Theory and Laboratory Experimentation

Factors influencing the response of total organic vapor detection instruments used in soil-gas surveying for subsurface gasoline leakage were investigated through performing theoretical assessments and laboratory experiments. Theoretical assessments indicate that total organic vapor measurements will depend on response conditions and the relative concentration of constituents in soil gas, in addition to absolute constituent levels. Laboratory tests conducted using flame ionization, photoionization and explosimeter devices indicated that conditions influencing their responses included instrument flow rate and soil-air permeability when performing direct-probe sampling; the linear range of the instrument; the multicomponent nature of gasoline vapors; and levels of oxygen, nitrogen, carbon dioxide and relative humidity in soil air. If an instrument's response to these conditions is not taken into account, survey results may be misleading. To circumvent adverse instrument responses, a serial dilution technique is presented.     

Observed Spatial and Temporal Distributions of CVOCs at Colorado and New York Vapor Intrusion Sites

The vapor intrusion impacts associated with the presence of chlorinated volatile organic contaminant plumes in the ground water beneath residential areas in Colorado and New York have been the subject of extensive site investigations and structure sampling efforts. Large data sets of ground water and indoor air monitoring data collected over a decade-long monitoring program at the Redfield, Colorado, site and monthly ground water and structure monitoring data collected over a 19-month period from structures in New York State are analyzed to illustrate the temporal and spatial distributions in the concentration of volatile organic compounds that one may encounter when evaluating the potential for exposures due to vapor intrusion. The analysis of these data demonstrates that although the areal extent of structures impacted by vapor intrusion mirrors the areal extent of chlorinated volatile organic compounds in the ground water, not all structures above the plume will be impacted. It also highlights the fact that measured concentrations of volatile organic compounds in the indoor air and subslab vapor can vary considerably from month to month and season to season. Sampling results from any one location at any given point in time cannot be expected to represent the range of conditions that may exist at neighboring locations or at other times. Recognition of this variability is important when designing sampling plans and risk management programs to address the vapor intrusion pathway.     

Acquisition of Representative Ground Water Quality Samples for Metals

R.S. Kerr Environmental Research Laboratory (RSKERL) personnel have evaluated sampling procedures for the collection of representative, accurate, and reproducible ground water quality samples for metals for the past four years. Intensive sampling research at three different field sites has shown that the method by which samples are collected has a greater impact on sample quality, accuracy, and reproducibility than whether the samples are filtered or not. In particular, sample collection practices that induce artificially high levels of turbidity have been shown to have the greatest negative impacts on sample quality. Results indicated the ineffectiveness of bailers for collection of representative metal samples. Inconsistent operator usage together with excessive purging generally resulted in excessive turbidity (>100 NTUs) and large differences in filtered and unfiltered metal samples. The use of low flow rate purging and sampling consistently produced filtered and unfiltered samples that showed no significant differences in concentrations. Turbidity levels were generally less than 5 NTUs, even in fine-textured glacial till. We recommend the use of low flow rates, during both purging and sampling, placement of the sampling intake at the desired sampling point, minimal disturbance of the stagnant water column above the screened interval, monitoring of water quality indicators during purging, minimization of atmospheric contact with samples, and collection of unfiltered samples for metal analyses to estimate total contaminant loading in the system. While additional time is spent due to use of low flow rates, this is compensated for by eliminating the need for filtration, decreased volume of contaminated purge water, and less resampling to address inconsistent data results.     

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.     

Development of a Default Vapor Intrusion Attenuation Factor for Industrial Buildings

An investigation at a major industrial facility in the Midwestern United States provides insights regarding the amount of attenuation of sub-surface vapors occurring at industrial buildings. The buildings at the facility were ranked in terms of vapor intrusion potential and testing began in October 2016 and is ongoing. Results have been evaluated for data collected at 718 unique locations across 77 buildings. A total of 1646 sample pairs (sub-slab and indoor air) have been collected and analyzed for 65 analytes, resulting in a total of 106,990 data pairs. As many as 49 sample pairs were collected within a given building during a single sampling event and up to 11 rounds of seasonal testing have been performed at selected buildings. Seasonal variability in sub-slab soil-gas concentrations was found to be negligible. Data analysis was performed to look for data trends across the entire data set and identify inter-building comparisons. This data evaluation focused on individual volatile organic compounds (e.g., tetrachloroethylene, trichloroethylene) present in the sub-slab soil gas at concentrations exceeding 1000 μg/m³. A total of 157 building-specific attenuation coefficients (α) were evaluated. This evaluation demonstrated that large industrial buildings have a much greater attenuation than that assumed for single-family residential buildings. All attenuation coefficient values were lower than 0.03, which is the standard regulatory default for non-residential buildings. The median value was 9.3E-05 and the 95% upper confidence limit was 2.7E-04. There is some evidence of lower attenuation under wintertime conditions. The data suggests that the default attenuation factor of 0.03 over-predicts indoor air impacts at this industrial facility by at least two orders of magnitude.     

Field Investigation of Vapor‐Phase‐Based Groundwater Monitoring

The use of in‐field analysis of vapor‐phase samples to provide real‐time volatile organic compound (VOC) concentrations in groundwater has the potential to streamline monitoring by simplifying the sample collection and analysis process. A field validation program was completed to (1) evaluate methods for collection of vapor samples from monitoring wells and (2) evaluate the accuracy and precision of field‐portable instruments for the analysis of vapor‐phase samples. The field program evaluated three vapor‐phase sample collection methods: (1) headspace samples from two locations within the well, (2) passive vapor diffusion (PVD) samplers placed at the screened interval of the well, and (3) field vapor headspace analysis of groundwater samples. Two types of instruments were tested: a field‐portable gas chromatograph (GC) and a photoionization detector (PID). Field GC analysis of PVD samples showed no bias and good correlation to laboratory analysis of groundwater collected by low‐flow sampling (slope = 0.96, R² = 0.85) and laboratory analysis of passive water diffusion bag samples from the well screen (slope = 1.03; R² = 0.96). Field GC analysis of well headspace samples, either from the upper portion of the well or at the water‐vapor interface, resulted in higher variability and much poorer correlation (consistently biased low) relative to laboratory analysis of groundwater samples collected by low‐flow sample or passive diffusion bags (PDBs) (slope = 0.69 to 0.76; R² = 0.60 to 0.64). These results indicate that field analysis of vapor‐phase samples can be used to obtain accurate measurements of VOC concentrations in groundwater. However, vapor samples collected from the well headspace were not in equilibrium with water collected from the well screen. Instead, PVD samplers placed in the screened interval represent the most promising approach for field‐based measurement of groundwater concentrations using vapor monitoring techniques and will be the focus of further field testing.     

Empirical Assessment of Ground Water–to-Indoor Air Attenuation Factors for the CDOT-MTL Denver Site

The area surrounding the Colorado Department of Transportation Materials Testing Laboratory in Denver was the subject of intense investigation, involving the collection of thousands of ground water, soil-gas, and indoor air samples in order to investigate indoor air impacts associated with a subsurface release of chlorinated solvents. The preremediation portion of that data set is analyzed and reduced in this work to ground water–to-indoor air attenuation factors (α_gw= the ratio of the measured indoor air concentration to the soil-gas concentration predicted to be in equilibrium with the local ground water concentration). The empirical α_gw values for this site range from about 10⁻⁶ to 10⁻⁴ with an overall average of 3 × 10⁻⁵ (μg/L indoor air)/(μg/L soil gas). The analysis of this data set highlights the need for a thorough data review and data screening when using large data sets to derive empirical relationships between subsurface concentrations and indoor air. More specifically, it is necessary to identify those parts of the data that contain a strong vapor intrusion pathway signal, which generally will require concentrations well above reported detection levels combined with spatial or temporal correlation of subsurface and indoor concentrations.     

Small Purge Method to Sample Vapor from Groundwater Monitoring Wells Screened Across the Water Table

Groundwater monitoring wells are present at most hydrocarbon release sites that are being assessed for cleanup. If screened across the vadose zone, these wells provide an opportunity to collect vapor samples that can be used in the evaluation of vapor movement and biodegradation processes occurring at such sites. This paper presents a low purge volume method (modified after that developed by the U.S. EPA) for sampling vapor from monitoring wells that is easy to implement and can provide an assessment of the soil gas total petroleum hydrocarbon (TPH) and O₂ concentrations at the base of the vadose zone. As a result, the small purge method allows for sampling of vapor from monitoring wells to support petroleum vapor intrusion (PVI) risk assessment. The small purge volume method was field tested at the Hal's service station site in Green River, Utah. This site is well‐known for numerous soil gas measurements containing high O₂ and high TPH vapor concentrations in the same samples which is inconsistent with well‐accepted biodegradation models for the vapor pathway. Using the low purge volume method, monitoring wells were sampled over, upgradient, and downgradient of the light nonaqueous phase liquid (LNAPL) footprint. Results from our testing at Hal's show that vapor from monitoring wells over LNAPL contained very low O₂ and high TPH concentrations. In contrast, vapor from monitoring wells not over LNAPL contained high O₂ and low TPH concentrations. The results of this study show that a low purge volume method is consistent with biodegradation models especially for sampling at sites where low permeability soils exist in and around a LNAPL source zone.     

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.     

Portable GC/MS Methods to Evaluate Sources of cVOC Contamination in Indoor Air

A portable gas chromatograph‐mass spectrometer (GC/MS) was used to investigate sources of chlorinated volatile organic compound (cVOC) contamination in indoor air at 46 residences around Hill AFB, Utah, that were potentially affected by vapor intrusion. Analytical methods were developed to allow sample turnaround times of less than 10 min and method detection limits (MDLs) generally less than 1 μg/m³ for a selected list of cVOCs. Area‐by‐area sampling was used to identify the likely vapor source locations. In many cases, individual container/enclosure sampling and subsequent field emission rate measurements from isolated consumer products were used to determine if identified products were likely to be the primary source of vapors in the residence. The portable GC/MS was also used to characterize vapor intrusion in two residences. In one of these two residences, building pressure control was used to enhance vapor entry in order to facilitate the investigation resulting in confirmation of vapor intrusion and identification of a primary route of vapor entry. cVOCs were identified in 42 of the 46 homes investigated, subsurface vapor intrusion was identified in two homes, and two homes had inconclusive results.     

A Method to Assess Analytical Uncertainties Over Large Concentration Ranges With Reference to Volatile Organics in Water

The uncertainty associated with a volatile organic concentration measurement is a function of variability and bias introduced at the various levels of sample handling: collection, storage, and analysis. During the past decade, sampling materials and the development and/or improvement of sampling protocols have been the subject of considerable research activity. As a result, in cases of samples properly handled, the analytical variability can be the dominant source of uncertainty in a given concentration value. Here analytical variability refers to any error that might arise during analysis, including the detector response error and any sample handling errors common to both standards and samples. This can be a particular concern for field analyses by gas chromatography (GC), Well-established statistical methods are available to estimate analytical uncertainty from linear calibration curves, but these methods are poorly suited for the analysis of volatile organics because organic samples frequently require instrument calibration (usually GC) over several orders of magnitude in concentration. If a single linear calibration curve is used to determine sample concentrations and uncertainties, then unrealistically large uncertainties may be assigned to low concentration samples. However, the methods can be adopted for extended concentration range calibration curves by breaking the overall calibration line down into smaller sub-calibration lines that span smaller ranges. These can then be examined and used selectively to determine concentrations with more appropriate uncertainties attached. The method of multiple callbration line analysis described here is suitable for programming with any high level computer language. It can be used to calculate meaningful analytical uncertainty values for any substance analyzed over a wide range in concentrations (i.e., an order of magnitude or more).     

Prediction of Indoor Air Quality from Soil-Gas Data at Industrial Buildings

Subslab or shallow soil-gas data are often compared with indoor air concentration data in vapor intrusion (VI) evaluations. If no indoor air data are available or confounding sources are present, or if future scenarios are considered, the soil-gas data may be used to estimate the indoor air concentrations due to VI. The typical approach in risk assessments is to use the 95th percentile values from a set of concentration data. For VI studies, however, this rarely is an option because the data sets tend to be quite small. Therefore, various guidance documents urge the use of maximum soil-gas values. This may be reasonable for small residential buildings, but can lead to very conservatively biased estimates if applied to large industrial buildings with localized areas of contamination, especially given that the sampling locations may not be randomly selected and instead are biased toward worst-case locations. By this approach, VI guidance implicitly tolerates a large percentage of false positive decision errors to minimize the number of false negative decision errors. In this paper, implications of using maximum values are discussed and illustrated with data sets from a number of large industrial buildings at various sites. An alternative approach to using maximum soil-gas values is proposed that serves to reduce the number of false positive results while controlling the number of false negatives to an acceptable level.     

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.     

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.