An evaluation of the performance of multiple passive diffusion devices for indoor air sampling of VOCs

The United States Environmental Protection Agency is considering recommending longer‐term sampling to achieve more accurate time‐weighted‐average detections for indoor air monitoring of volatile organic chemicals. The purpose of the research presented herein was to compare longer sampling times using passive diffusion samplers to the results from shorter‐term testing periods using sorbent tubes and low‐flow pumps (US EPA Method TO‐17) at great frequency for trichloroethene (TCE) in indoor air. A controlled release of TCE in a large room allowed for over two‐orders‐of‐magnitude daily concentration variability over the course of the two‐week monitoring event. The daily concentration measurements by US EPA Method TO‐17 and the passive diffusion samplers were performed in triplicate and had excellent reproducibility. The results of daily tests were averaged and compared with four passive diffusion devices exposed to indoor air for three, seven, ten, and fourteen days in accordance with ASTM D6196‐02. A specific uptake rate for each of the passive devices at the four different time intervals and the statistical significance of the time‐varying uptake rates were evaluated. The performance of each passive diffusion device was determined using a statistical performance criterion. The average concentration for all of the exposure periods could be reliably predicted using the established uptake rates for two of the four passive devices. © 2009 Wiley Periodicals, Inc.     

High‐Frequency Continuous Monitoring to Track Vapor Intrusion Resulting From Naturally Occurring Pressure Dynamics

Vapor intrusion characterization efforts can be challenging due to complexities associated with background indoor air constituents, preferential subsurface migration pathways, and response time and representativeness limitations associated with conventional low‐frequency monitoring methods. For sites experiencing trichloroethylene (TCE) vapor intrusion, the potential for acute risks poses additional challenges, as the need for rapid response to exposure exceedances becomes critical in order to minimize health risks and associated liabilities. Continuous monitoring platforms have been deployed to monitor indoor and subsurface concentrations of key volatile constituents, atmospheric pressure, and pressure differential conditions that can result in advective transport. These systems can be comprised of multiplexed laboratory‐grade analytical components integrated with telemetry and geographical information systems for automatically generating time‐stamped renderings of observations and time‐weighted averages through a cloud‐based data management platform. Integrated automatic alerting and responses can also be engaged within one minute of risk exceedance detection. The objectives at a site selected for testing included continuous monitoring of vapor concentrations and related surface and subsurface physical parameters to understand exposure risks over space and time and to evaluate potential mechanisms controlling risk dynamics which could then be used to design a long‐term risk reduction strategy. High‐frequency data collection, processing, and automated visualization efforts have resulted in greater understanding of natural processes such as dynamic contaminant vapor intrusion risk conditions potentially influenced by localized barometric pumping induced by temperature changes. For the selected site, temporal correlation was observed between dynamic indoor TCE vapor concentration, barometric pressure, and pressure differential. This correlation was observed with a predictable daily frequency even for very slight diurnal changes in barometric pressure and associated pressure differentials measured between subslab and indoor regimes and suggests that advective vapor transport and intrusion can result in elevated indoor TCE concentrations well above risk levels even with low‐to‐modest pressure differentials. This indicates that vapor intrusion can occur in response to diurnal pressure dynamics in coastal regions and suggests that similar natural phenomenon may control vapor intrusion dynamics in other regions, exhibiting similar pressure, geochemical, hydrogeologic, and climatic conditions. While dynamic indoor TCE concentrations have been observed in this coastal environment, questions remain regarding whether this hydrogeologic and climatic setting represent a special case, and how best to determine when continuous monitoring should be required to most appropriately minimize exposure durations as early as possible. ©2017 Wiley Periodicals, Inc.     

Vapor intrusion risk evaluation using automated continuous chemical and physical parameter monitoring

Vapor intrusion risk characterization efforts are challenging due to complexities associated with background indoor air constituents, preferential subsurface migration pathways, and representativeness limitations associated with traditional randomly timed time‐integrated sampling methods that do not sufficiently account for factors controlling concentration dynamics. The U.S. Environmental Protection Agency recommends basing risk related decisions on the reasonable maximum exposure (RME). However, with very few exceptions, practitioners have not been applying this criterion. The RME will most likely occur during upward advective flux conditions. As such, for RME determinations, it is important to sample when upward advective flux conditions are occurring. The most common vapor intrusion assessment efforts include randomly timed sample collection events, and therefore do not accurately yield RME estimates. More specifically, researchers have demonstrated that randomly timed sampling schemes can result in false negative determinations of potential risk corresponding to RMEs. For sites experiencing trichloroethylene (TCE) vapor intrusion, the potential for acute risks poses additional challenges, as there is a critical need for rapid response to exposure exceedances to minimize health risks and liabilities. To address these challenges, continuous monitoring platforms have been deployed to monitor indoor concentrations of key volatile constituents, atmospheric pressure, and pressure differential conditions that can result in upward toxic vapor transport and entry into overlying buildings. This article demonstrates how vapor intrusion RME‐based risks can be successfully and efficiently determined using continuous monitoring of concentration and parameters indicating upward advective chemical flux. Time series analyses from multiple selected 8‐ and 24‐hr time increments during upward advective TCE flux conditions were performed to simulate results expected from the most commonly employed sampling methods. These analyses indicate that, although most of the selected time increments overlap within the same 24‐hr window, results and conclusions vary. As such, these findings demonstrate that continuous monitoring of concentration and parameters such as differential pressure and determination of a time‐weighted concentration average over a selected duration when upward advective flux is occurring can allow for a realistic RME‐based risk estimate.     

Automated continuous monitoring and response to toxic subsurface vapors entering overlying buildings—Selected observations,implications and considerations

Vapor intrusion characterization and response efforts must consider four key interactive factors: background indoor air constituents, preferential vapor migration pathways, complex patterns of vapor distribution within buildings, and temporal concentration variability caused by pressure differentials within and exterior to structures. An additional challenge is found at sites contaminated by trichloroethylene (TCE), which in the United States has very low indoor air screening levels due to acute risk over short exposure durations for sensitive populations. Timely and accurate characterization of vapor intrusion has been constrained by traditional passive time‐averaging sampling methods. This article presents three case studies of a robust new methodology for vapor intrusion characterization particularly suited for sites where there is a critical need for rapid response to exposure exceedances to minimize health risks and liabilities. The new methodology comprises low‐detection‐level field analytical instrumentation with grab sample and continuous monitoring capabilities for key volatile constituents integrated with pressure differential measurements and web‐based reporting. The system also provides automated triggered alerts to project teams and capability for integration with engineered systems for vapor intrusion control. The three case studies illustrate key findings and lessons learned during system deployment at two sites undergoing characterization studies and one site undergoing thermal remediation of volatile contaminants.     

Remediation techniques for mitigating vapor intrusion from sewer systems to indoor air

Investigations at former dry cleaning sites in Denmark show that sewer systems often are a major vapor intrusion pathway for chlorinated solvents to indoor air. In more than 20 percent of the contaminated drycleaner sites in Central Denmark Region, sewer systems were determined to be a major vapor intrusion pathway. Sewer systems can be a major intrusion pathway if contaminated groundwater intrudes into the sewer and contamination is transported within the sewer pipe by water flow in either free phase or dissolved states. Additionally, the contamination can volatilize from the water phase or soil gas can intrude the sewer system directly. In the sewer, the gas phase can migrate in any direction by convective transport or diffusion. Indications of the sewer as a major intrusion pathway are:

• higher concentrations in the upper floors in buildings,
• higher concentrations in indoor air than expected from soil gas measurements,
• higher concentrations in bathrooms/kitchen than in living rooms,
• chlorinated solvents in the sewer system, and
• a pressure gradient from the sewer system to indoor air.

Measurements to detect whether or not the sewer system is an intrusion pathway are simple. In Central Denmark Region, the concentrations of contaminants are routinely measured in the indoor air at all floors, the outdoor air, behind the water traps in the building, and in the manholes close to the building. The indoor and outdoor air concentration, as well as concentrations in manholes, are measured by passive sampling on sorbent samplers over a 14‐day period, and the measurements inside the sewer system are carried out by active sampling using carbon tubes (sorbent samplers). Furthermore, the pressure gradient over the building slab and between the indoor air and the sewer system are also measured. A simple test is depressurization of the sewer system. Using this technique, the pressure gradient between the sewer system and the indoor air is altered toward the sewer system—the contamination cannot enter the indoor air through the sewer system. If the sewer system is a major intrusion pathway, the effect of the test can be observed immediately in the indoor air. Remediation of a sewer transported contamination can be:

• prevention of the contaminants from intruding into the sewer system or
• prevention of the contaminated gas in the sewer system from intruding into the indoor air.

Remediation techniques include the following:

• lining of the sewer piping to prevent the contamination from intruding into the sewer;
• sealing the sewer system in the building to prevent the contamination from the sewer system to intrude the indoor air;
• venting of manholes; and
• depressurizing the sewer system.

     

Vapor Intrusion Monitoring Method Cost Comparisons: Automated Continuous Analytical Versus Discrete Time‐Integrated Passive Approaches

Vapor intrusion characterization efforts are challenging due to complexities associated with indoor background sources, preferential subsurface migration pathways, indoor and shallow subsurface concentration dynamics, and representativeness limitations associated with manual monitoring and characterization methods. For sites experiencing trichloroethylene (TCE) vapor intrusion, the potential for acute risks poses additional challenges, as the need for rapid response to acute toxicity threshold exceedances is critical in order to minimize health risks and associated liabilities. Currently accepted discrete time‐integrated vapor intrusion monitoring methods that employ passive diffusion–adsorption and canister samplers often do not result in sufficient temporal or spatial sampling resolution in dynamic settings, have a propensity to yield false negative and false positive results, and are not able to prevent receptors from acute exposure risks, as sample processing times exceed exposure durations of concern. Multiple lines of evidence have been advocated for in an attempt to reduce some of these uncertainties. However, implementation of multiple lines of evidence do not afford rapid response capabilities and typically rely on discrete time‐integrated sample collection methods prone to nonrepresentative results due to concentration dynamics. Recent technology innovations have resulted in the deployment of continuous monitoring platforms composed of multiplexed laboratory grade analytical components integrated with quality control features, telemetry, geographical information systems, and interpolation algorithms for automatically generating geospatial time stamped renderings and time‐weighted averages through a cloud‐based data management platform. Automated alerts and responses can be engaged within 1 minute of a threshold exceedance detection. Superior temporal and spatial resolution also results in optimized remediation design and mitigation system performance confirmation. While continuous monitoring has been acknowledged by the regulatory community as a viable option for providing superior results when addressing spatial and temporal dynamics, until very recently, these approaches have been considered impractical due to cost constraints and instrumentation limitations. Recent instrumentation advancements via automation and multiplexing allow for rapid and continuous assessment and response from multiple locations using a single instrument. These advancements have reduced costs to the point where they are now competitive with discrete time‐integrated methods. In order to gain more regulatory and industry support for these viable options, there is an immediate need to perform a realistic cost comparison between currently approved discrete time‐integrated methods and newly fielded continuous monitoring platforms. Regulatory support for continuous monitoring platforms will result in more effectively protecting the public, provide property owners with information sufficient to more accurately address potential liabilities, reduce unnecessary remediation costs for situations where risks are minimal, lead to more effective and surgical remediation strategies, and allow practitioners to most effectively evaluate remediation system performance. To address this need, a series of common monitoring scenarios and associated assumptions were derived and cost comparisons performed. Scenarios included variables such as number of monitoring locations, duration, costs to meet quality control requirements, and number of analyses performed within a given monitoring campaign. Results from this effort suggest that for relatively larger sites where five or more locations will be monitored (e.g., large buildings, multistructure industrial complexes, educational facilities, or shallow groundwater plumes with significant spatial footprints under residential neighborhoods), procurement of continuous monitoring services is often less expensive than implementation of discrete time‐integrated monitoring services. For instance, for a 1‐week monitoring campaign, costs‐per‐analysis for continuous monitoring ranges from approximately 1 to 3 percent of discrete time‐integrated method costs for the scenarios investigated. Over this same one‐week duration, for discrete time‐integrated options, the number of sample analyses equals the number of data collection points (which ranged from 5 to 30 for this effort). In contrast, the number of analyses per week for the continuous monitoring option equals 672, or four analyses per hour. This investigation also suggests that continuous automated monitoring can be cost‐effective for multiple one‐week campaigns on a quarterly or semi‐annual basis in lieu of discrete time‐integrated monitoring options. In addition to cost benefits, automated responses are embedded within the continuous monitoring service and, therefore, provide acute TCE risk‐preventative capabilities that are not possible using discrete time‐integrated passive sampling methods, as the discrete time‐integrated services include analytical efforts that require more time than the exposure duration of concern. ©2016 Wiley Periodicals, Inc.     

Cost‐Effective Rapid and Long‐Term Screening of Chemical Vapor Intrusion (CVI) Potential: Across Both Space and Time

Reviews including the latest “data‐rich” chemical vapor intrusion‐radon (CVI‐Rn) studies indicate buildings/times can be “screened‐in” as having Rn‐evident‐susceptibility/priority for soil gas intrusion, and elevated‐potential for CVI concerns, or not. These screening methods can supplement conventional indoor‐air chemical sampling, under naturally varying conditions, by prioritizing buildings and times based on indoor Rn levels. Rn is a widespread, naturally occurring component of soil gas and a tracer of soil gas intrusion into the indoor air of overlying buildings. Rn is also an indicator for generally similar behavior of other components of near‐building soil gas, possibly including chemical contaminant vapors. Indoor Rn is easily measured at a low cost, allowing continuous observations from essentially all buildings with the potential for CVI across time. This presents cost savings and other benefits for all CVI stakeholders.     

The influence of seasonal vertical temperature gradients on no‐purge sampling of wells

Seasonal changes in ambient temperature create vertical temperature gradients in shallow groundwater (less than 15 m). These temperature gradients can affect in‐well flow dynamics that impact samples collected using no‐purge sampling methods. In late winter, the shallower water is colder, resulting in thermally mixed conditions and uniform contaminant concentrations. In late summer, the shallower water is warmer, resulting in thermally stratified conditions and contaminant distributions in the monitoring well more consistent with the distribution in the surrounding aquifer. The importance of seasonal temperature gradients on in‐well mixing was evaluated in two shallow monitoring wells in Houston, Texas. In each of the two wells, four vertically spaced passive diffusion samples collected in late winter showed a less than 1.3x difference in trichloroethene (TCE) concentration between depths, while the same sampling conducted in late summer showed greater than a 100x difference in TCE concentration between depths. A simple analytical model originally developed to predict vertical soil temperature profiles can also be used to predict the occurrence of thermally stratified and thermally mixed conditions in monitoring wells as a function of time and well depth. The results of this analysis and modeling suggest that shallow monitoring wells in most of the United States and Canada can have significantly different vertical concentration profiles within the well over the course of a year due to seasonal vertical temperature gradients. This can induce additional intra‐annual temporal variability on passive no‐purge sampling results from these shallow wells, potentially making it more difficult to discern true trends in the data. © 2012 Wiley Periodicals, Inc.     

Laboratory validation study of new vapor‐phase‐based approach for groundwater monitoring

Recent improvements in field‐portable analytical equipment allow accurate on‐site measurement of VOCs present in air at concentrations of less than 0.1 parts per million volume (ppmv). The objective of this project is to determine if the use of these instruments for vapor‐phase measurements of headspace in a monitoring well can serve as a reliable and accurate method for monitoring volatile organic compound (VOC) concentrations in groundwater under equilibrium conditions. As part of a comprehensive research project investigating the utility of this proposed monitoring method, the authors have completed a laboratory validation study to identify instruments and sample‐collection methods that will provide accurate measurement of VOC concentrations in groundwater. This laboratory validation study identified two field‐portable instruments (a gas chromatograph and a photoionization detector) with sufficient sensitivity to measure VOCs in groundwater at concentrations below typical monitoring standards (i.e., 1 to 5 μg/L). The accuracy and precision of these field instruments was sufficient to satisfy typical data‐quality objectives for laboratory‐based analysis. In addition, two sample‐collection methods were identified that yield vapor‐phase samples in equilibrium with water: direct headspace sampling and passive diffusion samplers. These sample‐collection methods allow the field instruments (which measure VOC concentrations in vapor‐phase samples) to be used to measure VOC concentrations in water. After further validation of these sample‐collection methods in the field, this monitoring method will provide a simple way to obtain accurate real‐time measurements of VOC concentrations in groundwater using inexpensive field‐portable analytical instruments. © 2009 Wiley Periodicals, Inc.     

Overview of state approaches to vapor intrusion: 2018

Regulatory requirements for the evaluation of vapor intrusion vary significantly among states. For site owners and responsible parties that have sites in different regulatory jurisdictions, one challenge is to know and understand how the requirements or expectations for vapor intrusion differ from one jurisdiction to the next. Differences in requirements can make it difficult to manage sites in a consistent manner across jurisdictions. Eklund, Folkes, et al. (2007, February, Environmental Manager, 10–14) published an overview of state guidance for vapor intrusion in 2007 that provided a detailed summary of pathway screening values and other key vapor intrusion policies. An update by Eklund, Beckley, et al. (2012, Remediation, 22, 7–20) was published in 2012, which expanded the evaluation to additional states. Since that time, numerous states have substantially revised their guidance and some states that did not have vapor intrusion‐specific guidance have issued new guidance. This article provides an update to the 2012 study. For each state, the review includes tabulations of the types of screening values included (e.g., groundwater, soil, soil gas, indoor air) and the screening values for selected chemicals that commonly drive vapor intrusion investigations (i.e., trichloroethylene [TCE], tetrachloroethylene, and benzene) along with other compounds of potential interest. In addition, for each state, the article summarizes a number of key policy decisions that are important for the investigation of vapor intrusion including: distance screening criteria, default subsurface to indoor air attenuation factors, mitigation criteria, and policies for evaluation of short‐term TCE exposure.     

Conceptual Site Model Development and Phased Remedy Implementation to Achieve Vapor Screening Goals at a Former Dry Cleaner

Tetrachloroethene (PCE) releases at a former dry cleaner resulted in impacts to soil and shallow groundwater beneath and adjacent to the building. Subsurface impacts led to vapor intrusion with PCE concentrations between 900 and 1,200 micrograms per cubic meter (μg/m³) in indoor air. The migration pathways of impacted soil vapor were evaluated through implementation of a helium tracer test and vapor sampling of an exterior concrete block wall. Results confirmed that the concrete block wall acted as a conduit for vapor intrusion into the building. A combination of remediation efforts focused on mass reduction in the source area as well as mitigation efforts to inhibit vapor migration into the building. Excavation of soils beneath the floor slab and installation of a spray‐applied vapor barrier resulted in PCE concentrations in indoor air decreasing by over 97.9 percent. Operation of an active ventilation system installed under the floor slab and groundwater remediation via injections of nano‐scale zero valent iron (nZVI) further reduced PCE concentrations in indoor air by over 99.8 percent compared to baseline conditions. While significant reductions of PCE concentrations in groundwater were observed within two months after injection, maximum reductions to PCE concentrations in indoor air were not observed for an additional 12 months. © 2014 Wiley Periodicals, Inc.     

MULTI INCREMENT® TCE vadose‐zone investigation

MULTI INCREMENT® and discrete sampling strategies were used to estimate the average concentration and the three‐dimensional distribution of TCE in a 3,300‐m³ zone composed of two decision units (e.g., area of concern, population, exposure unit). Authors of this article and a private contractor (Stanley Consultants Inc.), respectively, implemented these two sampling strategies independently. Compared to discrete sampling, the MULTI INCREMENT sampling strategy identified more locations where percent‐level concentrations of TCE have migrated, is more economical, and provided greater data quality. © 2008 Wiley Periodicals, Inc.     

Sampling strategies in the assessment of long‐term exposures to toxic substances in air

The decision to mitigate exposures from vapor intrusion (VI) is typically based on limited data from 24‐hour air samples. It is well documented that these data do not accurately represent long‐term average exposures linked to adverse health effects. Limited decision guidance is currently available to determine the most appropriate sampling strategy, considering the cost of sampling alternatives along with the economic consequences of exposure‐related health effects. We present a decision model that introduces economic and statistical considerations in evaluating alternative VI sampling methods. The model characterizes the best sampling method by factoring economic and health consequences of exposure, the variability of exposure, the cost of sampling and mitigation, and the likelihood of false‐negatives and false‐positives. Decision‐makers can use results to select the sample size that maximizes net benefit. Conceptual and mathematical models are presented linking biological, statistical, and economic considerations to assess the cost and effectiveness of different sampling strategies. The model relates an average exposure concentration, determined statistically, to abatement costs and to the monetary value of health deterioration. The value of the information provided by different strategies is calculated and used to select the optimum sampling method. Simulations show that longer‐term sampling methods tend to be more accurate and cost‐effective than short‐term samples. The ideal sampling strategy shows significant seasonal variation (it is typically optimal to use longer samples in the winter) and also varies significantly with the stringency of regulatory standards. Longer‐term sample collection provides a more accurate representation of average VI exposure and reduces the likelihood of type I and type II errors. This reduces expected costs of mitigation and exposure (e.g., health consequences, legal and regulatory penalties), which in some cases can be quite significant. The model herein shows how these savings are balanced against the additional costs of longer‐term sampling.     

Dynamic subsurface explosive vapor concentrations: Observations and implications

Conventional vapor intrusion characterization efforts can be challenging due to background indoor air constituents, preferential subsurface migration pathways, sampling access, and collection method limitations. While it has been recognized that indoor air concentrations are dynamic, until recently it was assumed by many practitioners that subsurface concentrations did not vary widely over time. Newly developed continuous monitoring platforms have been deployed to monitor subsurface concentrations of methane, carbon dioxide, oxygen, hydrogen sulfide, total volatile organic constituents, and atmospheric pressure. These systems have been integrated with telemetry, geographical information systems, and geostatistical algorithms for automatically generating two‐ and three‐dimensional contour images and time‐stamped renderings and playback loops of sensor attributes, and multivariate analyses through a cloud‐based project management platform. The objectives at several selected sites included continuous monitoring of vapor concentrations and related physical parameters to understand explosion risks over space and time and to then design a long‐term risk reduction strategy. High‐frequency data collection, processing, and automated visualization have resulted in greater understanding of natural processes, such as dynamic contaminant vapor intrusion risk conditions potentially influenced by localized barometric pumping. For instance, contemporaneous changes in methane, oxygen, and atmospheric pressure values suggest there is interplay and that vapor intrusion risk may not be constant. As a result, conventional single‐event and composite assessment technologies may not be capable of determining worst‐case risk scenarios in all cases, possibly leading to misrepresentation of receptor and explosion risks. While dynamic risk levels have been observed in several initial continuous monitoring applications, questions remain regarding whether these situations represent special cases and how best to determine when continuous monitoring should be required. Results from a selected case study are presented and implications derived. © 2011 Wiley Periodicals, Inc.     

ERD of Residual TCE DNAPL Achieving Nondetect from a Single Injection of Food‐Grade Waste

Residual dense nonaqueous phase liquid (DNAPL) composed of trichloroethene (TCE) was identified in a deeper interval of an overburden groundwater system at a manufacturing facility located in northern New England. Site hydrostratigraphy is characterized by two laterally continuous and transmissive zones consisting of fully‐saturated fine sand with silt and clay. The primary DNAPL source was identified as a former dry well with secondary contributions from a proximal aboveground TCE storage tank. A single additive‐injection mobilization in 2001 utilizing a food‐grade injectate formulated with waste dairy product and inactive yeast enhanced residual TCE DNAPL destruction in situ by stimulating biotic reductive dechlorination. The baseline TCE concentration was detected up to 97,400 μg/L in the deeper interval of the overburden groundwater system, and enhanced reductive dechlorination (ERD) achieved >99 percent reduction in TCE concentrations in groundwater over nine years with no evidence of sustained rebound. TCE concentrations have remained nondetect below 2.0 μg/L for the last five consecutive sampling rounds between 2013 and 2015. ERD utilizing a food‐grade injectate is a green remediation technology that has destroyed residual DNAPL at the site and achieved similar results at other residual DNAPL sites during both pilot‐ and full‐scale applications. ©2016 Wiley Periodicals, Inc.     

Optimizing remediation strategies for a former dry‐cleaner site

Residual tetrachloroethene (PCE) contamination at the former Springvilla Dry Cleaners site in Springfield, Oregon, posed a potential risk through the vapor intrusion, direct contact, and off‐site beneficial groundwater uses. The Oregon Department of Environmental Quality utilized the State Dry Cleaner Program funds to help mitigate the risks posed by residual contamination. After delineation activities were complete, the source‐area soils were excavated and treated on‐site with ex situ vapor extraction to reduce disposal costs. Residual source‐area contamination was then chemically oxidized using sodium permanganate. Dissolved‐phase contamination was subsequently addressed with in situ enhanced reductive dechlorination (ERD). ERD achieved treatment goals across more than 4 million gallons of aquifer impacted with PCE concentrations up to 7,800 micrograms per liter prior to remedial activities. The ERD remedy introduced electron donors and nutrient amendments through groundwater recirculation and slug injection across two aquifers over the course of 24 months. Adaptive and mass‐targeted strategies reduced total remedy costs to approximately $18 per ton within the treatment areas. © 2010 Wiley Periodicals, Inc.     

Seven‐year performance evaluation of a permeable reactive barrier

In June and July 2001, the Massachusetts Department of Environmental Protection (MassDEP) installed a permeable reactive barrier (PRB) to treat a groundwater plume of chlorinated solvents migrating from an electronics manufacturer in Needham, Massachusetts, toward the Town of Wellesley's Rosemary Valley wellfield. The primary contaminant of concern at the site is trichloroethene (TCE), which at the time had a maximum average concentration of approximately 300 micrograms per liter directly upgradient of the PRB. The PRB is composed of a mix of granular zero‐valent iron (ZVI) filings and sand with a pure‐iron thickness design along its length between 0.5 and 1.7 feet. The PRB was designed to intercept the entire overburden plume; a previous study had indicated that the contaminant flux in the bedrock was negligible. Groundwater samples have been collected from monitoring wells upgradient and downgradient of the PRB on a quarterly basis since installation of the PRB. Inorganic parameters, such as oxidation/reduction potential, dissolved oxygen, and pH, are also measured to determine stabilization during the sampling process. Review of the analytical data indicates that the PRB is significantly reducing TCE concentrations along its length. However, in two discrete locations, TCE concentrations show little decrease in the downgradient monitoring wells, particularly in the deep overburden. Data available for review include the organic and inorganic analytical data, slug test results from nearby bedrock and overburden wells, and upgradient and downgradient groundwater‐level information. These data aid in refining the conceptual site model for the PRB, evaluating its performance, and provide clues as to the reasons for the PRB's underperformance in certain locations. © 2008 Wiley Periodicals, Inc.     

Matrix Diffusion Modeling Applied to Long‐Term Pump‐and‐Treat Data: 1. Method Development

Despite the installation in the 1980s and 1990s of hydraulic containment systems around known source zones (four slurry walls and ten pump‐and‐treat systems), trichloroethene (TCE) plumes persist in the three uppermost groundwater‐bearing units at the Middlefield‐Ellis‐Whisman (MEW) Superfund Study Area in Mountain View, California. In analyzing TCE data from 15 recovery wells, the observed TCE mass discharge decreased less than an order of magnitude over a 10‐year period despite the removal of an average of 11 pore volumes of affected groundwater. Two groundwater models were applied to long‐term groundwater pump‐and‐treat data from 15 recovery wells to determine if matrix diffusion could explain the long‐term persistence of a TCE plume. The first model assumed that TCE concentrations in the plume are controlled only by advection, dispersion, and retardation (ADR model). The second model used a one‐dimensional diffusion equation in contact with two low‐permeability zones (i.e., upper and lower aquitard) to estimate the potential effects of matrix diffusion of TCE into and out of low‐permeability media in the plume. In all 15 wells, the matrix diffusion model fit the data much better than the ADR model (normalized root mean square error of 0.17 vs. 0.29; r² of 0.99 vs. 0.19), indicating that matrix diffusion is a likely contributing factor to the persistence of the TCE plume in the non‐source‐capture zones of the MEW Study Area's groundwater‐extraction wells. © 2013 Wiley Periodicals, Inc.     

Chlorinated vapor intrusion indicators,tracers, and surrogates (ITS): Supplemental measurements for minimizing the number of chemical indoor air samples—Part 1: Vapor intrusion driving forces and related environmental factors

Vapor intrusion (VI) assessment is complicated by spatial and temporal variability, largely due to compounded interactions among the many individual factors that influence the vapor migration pathway from subsurface sources to indoor air. Past research on highly variable indoor air datasets demonstrates that conventional sampling schemes can result in false negative determinations of potential risk corresponding to reasonable maximum exposures (RME). While high‐frequency chemical analysis of individual chlorinated volatile organic compounds (CVOCs) in indoor air is conceptually appealing, it remains largely impractical when numerous buildings are involved and particularly for long‐term monitoring. As more is learned about the challenges with indoor air sampling for VI assessment, it has become clear that alternative approaches are needed to help guide discrete sampling efforts and reduce sampling requirements while maintaining acceptable confidence in exposure characterization. Indicators, tracers, and surrogates (ITS), which include a collection of quantifiable metrics and tools, have been suggested as a potential solution for making VI pathway assessment and long‐term monitoring more informative, efficient, and cost‐effective. This review, compilation, and evaluation of ITS demonstrates how even low numbers of indoor air CVOC samples can provide high levels of confidence for representing the RME levels (e.g., 95th percentile) often sought by regulatory agencies for less than chronic effects. A two‐part compilation of available evidence for select low‐cost ITS is presented, with Part 1 focused on introducing the concepts of ITS, meteorologically based ITS, and the evidence from data‐rich studies to support lower cost CVOC VI assessments. Part 1 includes the results of quantitative analyses on two robust residential building VI datasets, where numerous supplemental metrics were collected concurrently with indoor air concentration data. These are supplemented with additional less‐intensive studies in different circumstances. These analyses show that certain ITS metrics and tools, including differential temperature, differential pressure, and radon (in Part 2), can provide benefits to VI assessment and long‐term monitoring. This includes indicators that narrow the assessment period needed to capture RME conditions, tracers that enhance understanding of the conceptual site model, and aid in the identification of preferential pathways and surrogates that support or substitute for CVOC sampling results. The results of this review provide insight into the scientifically supportable uses of ITS.     

Remediating TCE‐contaminated groundwater in low‐permeability media using hydraulic fracturing to emplace zero‐valent iron/organic carbon amendment

A field pilot test in which hydraulic fracturing was used to emplace granular remediation amendment (a mixture of zero‐valent iron [ZVI] and organic carbon) into fine‐grained sandstone to remediate dissolved trichloroethene (TCE)‐contaminated groundwater was performed at a former intercontinental ballistic missile site in Colorado. Hydraulic fracturing was used to enhance the permeability of the aquifer with concurrent emplacement of amendment that facilitates TCE degradation. Geophysical monitoring and inverse modeling show that the network of amendment‐filled fractures extends throughout the aquifer volume targeted in the pilot test zone. Two years of subsequent groundwater monitoring demonstrate that amendment addition resulted in development of geochemical conditions favorable to both abiotic and biological TCE degradation, that TCE concentrations were substantially reduced (i.e., greater than 90 percent reduction in TCE mass), and that the primary degradation processes are likely abiotic. The pilot‐test data aided in re‐evaluating the conceptual site model and in designing the full‐scale remedy to address a larger portion of the TCE‐contaminated groundwater plume. © 2012 Wiley Periodicals, Inc.