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.     

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 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.     

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.     

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.     

Demonstration of a Microbiologically Enhanced Vertical Ground Water Circulation Well Technology at a Superfund Site

A full-scale ground water circulation well (GCW) system was installed and operated to demonstrate in situ remediation of soil and ground water impacted with a mixture of chlorinated and nonchlorinated organic compounds at a Superfund site in upstate New York. System performance and applicability under site-specific conditions were evaluated based on the system's ability to meet the New York State Department of Environmental Conservation (NYSDEC) cleanup goals for target compounds in ground water and soil. Contaminants from the unsaturated zone were mobilized (volatilized) by one-way vacuum extraction, and treated via enhanced biodegradation (bioventing). In the saturated zone, contaminants were mobilized by soil flushing (solubilized) and treated by a combination of air stripping and biodegradation. An in situ aqueous phase bioreactor, and an ex situ gas phase bioreactor, were integrated into the system to enhance treatment via bioremediation. After 15 months of operation, the mass of target contaminants in soil and ground water combined had been reduced by 75%. Removal by biological mechanisms ranged from 35% to 56% of the total observed mass reduction. The in situ and the ex situ bioreactors mineralized 79% and 76%, respectively, of their target biodegradable contaminant loads. Results indicate that some mass reduction in target contaminants may have been from aerobic and aerobic processes within the circulation cell. Nonchlorinated compounds were relatively easy to mobilize (volatilize, solubilize, and/or transport) and treat when compared to chlorinated compounds. The data collected during the 15-month study indicate that remediation could be accomplished at the Sweden-3 Chapman site using the technology tested.     

Observation of Conditions Preceding Peak Indoor Air Volatile Organic Compound Concentrations in Vapor Intrusion Studies

Temporal and spatial variability of indoor air volatile organic compound (VOC) concentrations can complicate vapor intrusion (VI) assessment and decision-making. Indicators and tracers (I&T) of VI, such as differential temperature, differential pressure, and indoor radon concentration, are low-cost lines of evidence to support sampling scheduling and interpretation of indoor air VOC sampling results. This study compares peak indoor air chlorinated VOC concentrations and I&T conditions before and during those peak events at five VI sites. The sites differ geographically and in their VI conceptual site models (CSM). Relative to site-specific baseline values, the results show that cold or falling outdoor temperatures, rising cross slab differential pressures, and increasing indoor radon concentrations can predict peak VOC concentrations. However, cold outdoor air temperature was not useful at one site where elevated shallow soil temperature was a better predictor. Correlations of peak VOC concentrations to elevated or rising barometric pressure and low wind speed were also observed with some exceptions. This study shows how the independent variables that control or predict peak indoor air VOC concentrations are specific to building types, climates, and VI CSMs. More I&T measurements at VI sites are needed to identify scenario-specific baseline and peak related I&T conditions to improve decision-making.     

An Evaluation of Some Systems for Sampling Gas-Charged Ground Water for Volatile Organic Analysis

Loss of volatile organics during sampling is a well-recognized source of bias in ground water monitoring; sampling protocols attempt to minimize such loss. Such bias could be enhanced for ground water highly charged with dissolved gases such as methane. Such ground water was the object of this study. A positive-displacement bladder pump, a momentum-lift pump and a suction-lift, peristaltic pump were employed in sampling both methane-charged ground water for volatile aromatic hydrocarbons and a CO₂-charged reservoir water for volatile chlorinated hydrocarbons. In both cases, the suction-lift pump produced samples with a significant negative bias (9 to 33 percent) relative to the other methods. Little difference between samples produced by the other pump Systems was noted at the field site, but in sampling the reservoir, the bladder pump produced samples that were 13 to 19 percent lower in halocarbon concentration than were samples from the momentum-lift pump.
These negative biases are tentatively interpreted as losses due to volatilization during sampling. Slightly greater negative biases occur for compounds of higher volatility as estimated from their Henry's law constants. Additional studies appear to be warranted in order to adequately establish the scientific basis for recommending protocols for sampling ground water in which degassing could enhance the loss of volatile organics during sampling.     

A Case Study of Soil-Gas Sampling in Silt and Clay-Rich (Low-Permeability) Soils

Soil-gas sampling and analysis is a common tool used in vapor intrusion assessments; however, sample collection becomes more difficult in fine-grained, low-permeability soils because of limitations on the flow rate that can be sustained during purging and sampling. This affects the time required to extract sufficient volume to satisfy purging and sampling requirements. The soil-gas probe tubing or pipe and sandpack around the probe screen should generally be purged prior to sampling. After purging, additional soil gas must be extracted for chemical analysis, which may include field screening, laboratory analysis, occasional duplicate samples, or analysis for more than one analytical method (e.g., volatile organic compounds and semivolatile organic compounds). At present, most regulatory guidance documents do not distinguish between soil-gas sampling methods that are appropriate for high- or low-permeability soils. This paper discusses permeability influences on soil-gas sample collection and reports data from a case study involving soil-gas sampling from silt and clay-rich soils with moderate to extremely low gas permeability to identify a sampling approach that yields reproducible samples with data quality appropriate for vapor intrusion investigations for a wide range of gas-permeability conditions.     

Use of Total Organic Carbon as an Indicator of Contamination from an Oil Refinery, South-Central Kansas

Water samples collected from 26 sites at an abandoned oil refinery in south-central Kansas were analyzed for total organic carbon (TOC) and specific volatile and semivolatile organic compounds by gas-chromatography/mass-spectrometric methods. Results from a Spearman-rho correlation analysis between TOC concentration and the number of compounds (correlation coefficient = 0.71) and TOC concentration and total concentration of compounds identified (correlation coefficient = 0.83) indicate correlations significant at the 0.01 level.
Although TOC data alone would not be sufficient to evaluate hazards posed by oil-refinery wastes, results of the correlation analysis performed using data collected from the site in Kansas indicate that TOC data can be used effectively to delineate petroleum-related ground water contamination and to help identify sources of ground water contaminants. TOC data collected from a large number of temporary sampling points during the initial phases of an investigation will provide an estimate of the extent of hydrocarbon contamination and allow placement of monitoring wells and more detailed sampling in appropriate areas.     

Evidence for Increasing Indoor Sources of 1,2-Dichloroethane Since 2004 at Two Colorado Residential Vapor Intrusion Sites

Groundwater contamination associated with two former industrial facilities in Denver, Colorado, has led to concerns about vapor intrusion into residences adjacent to the facilities. 1,1,1-Trichloroethane (1,1,1-TCA), 1,1-dichloroethene (1,1-DCE), and trichloroethene (TCE) are the main contaminants of concern in groundwater, with trace levels of 1,2-dichloroethane (1,2-DCA) present at one of the sites. Indoor air monitoring programs have been ongoing at these two sites since 1998 and recent results have suggested that background, indoor source, 1,2-DCA has been increasing in the frequency of detection, and median and maximum concentration over the past several years. A lines of evidence evaluation was undertaken for both sites in order to document the predominance of indoor sources of 1,2-DCA. Evidence utilized included spatial evaluation of 1,2-DCA in indoor air; comparison of 1,2-DCA concentrations in mitigated and unmitigated homes; a phone survey to evaluate the potential for smoking to contribute to indoor air 1,2-DCA levels; evaluation of mitigation system effluent data; and an evaluation of volatile organic compound (VOC) ratios in groundwater and indoor air. The results of this evaluation indicated that smoking had no demonstrable influence on measured indoor air concentrations. In addition, it appears that consumer products have had a markedly increased influence on indoor air concentrations since 2005. Data from one of the industrial facilities at one of the sites also indicated that polyvinyl chloride (PVC) and vinyl composite floor adhesive used in a building remodel in 2005 apparently generated elevated levels of indoor 1,2-DCA and vinyl chloride, which have been sustained up to the present time.     

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.     

Cone Penetrometer Tests and HydroPunch® Sampling: A Screening Technique for Plume Definition

Cone penetrometer tests and HydroPunch® sampling were used to define the extent of volatile organic compounds in ground water. The investigation indicated that the combination of these techniques is effective for obtaining ground water samples for preliminary plume definition. HydroPunch samples can be collected in unconsolidated sediments and the analytical results obtained from these samples are comparable to those obtained from adjacent monitoring wells. This sampling method is a rapid and cost-effective screening technique for characterizing the extent of contaminant plumes in soft sediment environments. Use of this screening technique allowed monitoring wells to be located at the plume boundary, thereby reducing the number of wells installed and the overall cost of the plume definition program.     

The Sensitivity of Four Monitoring Well Sampling Systems to Low Concentrations of Three Volatile Organics

Four state-of-the-art ground water sampling systems were analyzed to determine their reliability in providing representative samples of the volatile chlorinated hydrocarbons trichloroethylene (TCE), perchloroethylene (PCE), and 1,1,1-trichloroethane (TCA) from a simulated monitoring well. The sampling systems studied represent four commonly used devices, including a stainless steel and Teflon® piston pump, a Teflon bailer, a Teflon bladder pump, and a PVC air-lift pump.
Controlled laboratory sampling experiments were conducted in a tank and well test chamber designed to approximate field conditions. A well purging and sampling procedure was used in the test apparatus to determine the accuracy and precision of each device for detecting low concentrations of the compounds in ground water. The compounds selected are some of the most ubiquitous hazardous contaminants found in shallow aquifers near hazardous waste sites throughout the United States.
No significant statistical difference was found among the four sampling systems in detecting the compounds.     

The Occurrence of Appendix IX Organic Constituents in Disposal Site Ground Water

Monitoring data from 479 disposal site investigations were used to provide an initial estimate of the occurrence and distribution of 208 Appendix IX organic constituents in ground water. The most prevalent class of contaminants were the volatile organic compounds, which accounted for 84 percent of all the detectable events in the composite data set involving Appendix IX organic constituents. The abundance of the remaining subsets of Appendix IX organic constituents decreased in the following order: base/neutral compounds (8.6 percent), acid extractable compounds (3.5 percent), pesticides (3.0 percent), RCRA pesticides (0.6 percent), and non-priority pollutants (0.25 percent). A total of 66 Appendix IX organic constituents, including one volatile compound, two pesticides, three base/neutral compounds, and 60 non-priority pollutant compounds were not detected in any of the waste disposal site ground water monitoring records that were reviewed.
The current regulatory requirement to monitor for Appendix IX organic constituents is approximately four times more expensive than monitoring for conventional priority pollutants (volatile, base/neutral, acid extractable, and pesticide compounds). Because the non-priority pollutant compounds account for an estimated 76 percent of the Appendix IX analytical costs but only 0.25 percent of the detectable events in disposal site ground water, it has been recommended that this class of compounds be deleted from routine monitoring programs. A scaling back of the current requirement to the conventional priority pollutants would still target more than 99 percent of the Appendix IX organic constituent occurrences in ground water and result in an analytical cost savings of approximately $2750 per sample or an estimated $51 million a year without significantly reducing the volume of useful organic monitoring data that would be generated to assess ground water conditions in the vicinity of waste disposal sites.     

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.     

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 (VQCs). 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 α_m were approximately two orders of magnitude less than the α_p'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.     

A Comparison of Ground Water Monitoring Data from CERCLA and RCRA Sites

Ground water quality data generated during the investigation of 334 hazardous waste disposal sites were used to contrast the Resource Conservation and Recovery Act (RCRA) and Comprehensive Emergency Response, Compensation and Liability Act (CERCLA) monitoring. programs. The minimum RCRA-required network of four wells was equaled or exceeded at 94 percent of the 156 RCRA sites and 70 percent of the 178 CERCLA sites in the data base. A sampling frequency of four events per year or more was used at 60 percent of the RCRA sites compared to only 24 percent at the CERCLA sites. CERCLA records compiled to date indicate that 480 compounds have been detected and another 220 compounds have been tentatively identified in ground water in the vicinity of hazardous waste disposal sites. However, the composite data from 123 RCRA site monitoring programs only indicates the presence of 100 chemical substances. The most significant discrepancy in the RCRA detection monitoring program is that it only generates data on three of the 20 organic contaminants that have been most frequently detected during the CERCLA hazardous waste disposal site investigations. Modification of the current RCRA program to include routine analysis for volatile organic compounds would correct this weakness.     

A Compilation of Statistics for VOCs from Post-1990 Indoor Air Concentration Studies in North American Residences Unaffected by Subsurface Vapor Intrusion

This paper provides a summary of a number of indoor air quality studies reporting concentrations of volatile organic compounds (VOCs) in indoor air samples collected from residential properties in North America and provides average values for certain statistics (percentiles, detection frequency, maximum). This compilation includes several VOCs that are commonly assessed in studies of subsurface vapor intrusion to indoor air, but may also be attributable to consumer products, building materials, or even outdoor air (ambient) sources, specifically benzene, carbon tetrachloride, chloroform, 1,1-dichloroethane, 1,1-dichloroethene, 1,2-dichloroethane, cis and trans-1,2-dichloroethene, ethylbenzene, methyl tert-butyl ether, methylene chloride, tetrachloroethene, trichloroethene, toluene, trichloro-1,2,2-trifluoroethane, 1,1,1-trichloroethane, vinyl chloride, and meta, para, and ortho-xylene. In studies spanning 1990 through 2005, eleven of these compounds were detected in more than 50% of samples collected, and for several compounds (benzene, carbon tetrachloride, chloroform, ethylbenzene, and tetrachloroethene) the lower and upper quintiles of the indoor air concentrations are within the range of typical risk-based target levels. These summary statistics may help interpret data collected during a vapor intrusion investigation and communicate the findings of indoor air quality studies to building occupants and other stakeholders. Similar studies have been published in the past, but there has been a gradual change in indoor air quality over time and a large amount of new data has been collected, so this paper provides more relevant information for current use than previous compilations.     

Design, Installation, and Uses of Combination Ground Water and Gas Sampling Wells

Waste disposal sites with volatile organic compounds (VOCs) frequently contain contaminants that are present in both the ground water and vadose zone. Vertical sampling is useful where transport of VOCs in the vadose zone may effect ground water and where steep vertical gradients in chemical concentrations are anticipated. Designs for combination ground water and gas sampling wells place the tubing inside the casing with the sample port penetrating the casing for sampling. This physically interferes with pump or sampler placement. This paper describes a well design that combines a ground water well with gas sampling ports by attaching the gas sampling tubing and ports to the exterior of the casing. Placement of the tubing on the exterior of the casing allows exact definition of gas port depth, reduces physical interference between the various monitoring equipment, and allows simultaneous remediation and monitoring in a single well. The usefulness and versatility of this design was demonstrated at the Idaho National Engineering and Environmental Laboratory (INEEL) with the installation of seven wells with 53 gas ports, in a geologic formation consisting of deep basalt with sedimentary interbeds at depths from 7.2 to 178 m below land surface. The INEEL combination well design is easy to construct, install, and operate.