Characterizing In Situ Methane‐Enhanced Biostimulation Potential for 1,4‐Dioxane Biodegradation in Groundwater

This study characterizes the 1,4‐dioxane biodegradation potential for an in situ methane‐enhanced biostimulation field pilot study conducted at Air Force Plant 44, located south of the Tucson International Airport in Arizona. In this study, the use of methane as the primary substrate in aerobic cometabolic biodegradation of 1,4‐dioxane is evaluated using environmental molecular diagnostic tools. The findings are compared to an adjacent pilot study, wherein methane was generated via enhanced reductive dechlorination and where methane monooxygenase and methane‐oxidizing bacteria were also found to be abundant. This article also presents the use of ¹³C and ²H isotopic ratio enrichment, a more recent tool, to support the understanding of 1,4‐dioxane biodegradation in situ. This study is the first of its kind, although alkane gas‐enhanced biodegradation of 1,4‐dioxane has been evaluated extensively in microcosm studies and propane‐enhanced biodegradation of 1,4‐dioxane has been previously studied in the field. ©2016 Wiley Periodicals, Inc.     

1,4‐Dioxane: Emerging technologies for an emerging contaminant

The synthetic chemical, 1,4‐dioxane, is classified by the U.S. Environmental Protection Agency (EPA) as a probable human carcinogen. Between 2013 and 2015, the EPA detected 1,4‐dioxane in public drinking water supplies in 45 states at concentrations up to 33 µg/L and in groundwater from releases at hazardous waste sites across the United States. Although a Federal maximum contaminant level drinking water standard has not yet been proposed, state‐specific standards and criteria are as low as 0.3 µg/L. 1,4‐Dioxane is a recalcitrant chemical in that applications of conventional treatment technologies have had limited success in reducing concentrations in water to meet current and proposed health‐protective levels. Although mainly used as a stabilizer for the solvent 1,1,1‐trichloroethane, it has been used in other industrial processes and has been detected in a variety of consumer products, such as foods, pharmaceuticals, cosmetics, and detergents. The high aqueous solubility of 1,4‐dioxane coupled with limited solubility of chlorinated solvents typically found in conjunction with 1,4‐dioxane contamination is the primary reason for its treatment challenges. In the last several years, an alternative, cost‐effective technology has been developed that has demonstrated treatment to levels significantly lower than the Federal and state‐specific goals. This article provides a Federal and state‐by‐state summary of 1,4‐dioxane‐specific drinking water and groundwater concentration criteria and qualitative comparison of the effectiveness of conventional treatment technologies compared to the effectiveness of an alternative treatment technology. A case study is also provided to present details regarding the application of an alternative treatment technology at an active groundwater remediation site in California.     

Stable Isotope Probing to Confirm Field‐Scale Co‐Metabolic Biodegradation of 1,4‐Dioxane

1,4‐Dioxane, a common co‐contaminant with chlorinated solvents, is present in groundwater at Site 24 at Vandenberg Air Force Base in California. Historical use of chlorinated solvents resulted in concentrations of 1,4‐dioxane in groundwater up to approximately 2,000 μg/L. Starting in 2013, an in situ propane biosparge system operation demonstrated reductions in 1,4‐dioxane concentrations in groundwater. The work detailed herein extends the efforts of the first field demonstration to a second phase and confirms the biodegradation mechanism via use of stable isotope probing (SIP). After two months of operation, 1,4‐dioxane concentrations decreased approximately 45 to 83 percent at monitoring locations in the test area. The results of the SIP confirmed ¹³C‐enriched 1,4‐dioxane was transformed into dissolved inorganic carbon (suggesting mineralization to carbon dioxide) and incorporated into microbial biomass (likely attributed to metabolic uptake of biotransformation intermediates or of carbon dioxide).  ©2016 Wiley Periodicals, Inc.     

ART in‐well technology proves effective in treating 1,4‐dioxane contamination

A common industrial solvent additive is 1,4‐dioxane. Contamination of dissolved 1,4‐dioxane in groundwater has been found to be recalcitrant to removal by conventional, low‐cost remedial technologies. Only costly labor and energy‐intensive pump‐and‐treat remedial options have been shown to be effective remedies. However, the capital and extended operation and maintenance costs render pump‐and‐treat technologies economically unfeasible at many sites. Furthermore, pump‐and‐treat approaches at remediation sites have frequently been proven over time to merely achieve containment rather than site closure. A major manufacturer in North Carolina was faced with the challenge of cleaning up 1,4‐dioxane and volatile organic compound–impacted soil and groundwater at its site. Significant costs associated with the application of conventional approaches to treating 1,4‐dioxane in groundwater led to an alternative analysis of emerging technologies. As a result of the success of the Accelerated Remediation Technologies, LLC (ART) In‐Well Technology at other sites impacted with recalcitrant compounds such as methyl tertiarybutyl ether, and the demonstrated success of efficient mass removal, an ART pilot test was conducted. The ART Technology combines in situ air stripping, air sparging, soil vapor extraction, enhanced bioremediation/oxidation, and dynamic subsurface groundwater circulation. Monitoring results from the pilot test show that 1,4‐dioxane concentrations were reduced by up to 90 percent in monitoring wells within 90 days. The removal rate of chlorinated compounds from one ART well exceeded the removal achieved by the multipoint soil vapor extraction/air sparging system by more than 80 times. © 2005 Wiley Periodicals, Inc.     

Sustainable Remediation Considerations for Treatment of 1,4‐Dioxane in Groundwater

1,4‐Dioxane remediation is challenging due to its physiochemical properties and low target treatment levels. As such, applications of traditional remediation technologies have proven ineffective. There are a number of promising remediation technologies that could potentially be scaled for successful application to groundwater restoration. Sustainable remediation is an important consideration in the evaluation of remediation technologies. It is critically important to consider sustainability when new technologies are being applied or new contaminants are being treated with traditional technologies. There are a number of social, economic, and environmental drivers that should be considered when implementing 1,4‐dioxane treatment technologies. This includes evaluating sustainability externalities by considering the cradle‐to‐grave impacts of the chemicals, energy, processes, transportation, and materials used in groundwater treatment. It is not possible to rate technologies as more or less sustainable because each application is context specific. However, by including sustainability thinking into technology evaluations and implementation plans, decisions makers can be more informed and the results of remediation are likely to be more effective and beneficial. There are a number sustainable remediation frameworks, guidance documents, footprint assessment tools, life cycle assessment tools, and best management practices that can be utilized for these purposes. This paper includes an overview describing the importance of sustainability in technology selection, identifies sustainability impacts related to technologies that can be used to treat 1,4‐dioxane, provides an approximating approach to assess sustainability impacts, and summarizes potential sustainability impacts related to promising treatment technologies. ©2016 Wiley Periodicals, Inc.     

In situ thermal remediation of DNAPL and LNAPL using electrical resistance heating

Electrical resistance heating (ERH) is an in situ treatment for soil and groundwater remediation that can reduce the time to clean up volatile organic compounds (VOCs) from years to months. The technology is now mature enough to provide site owners with both performance and financial certainty in their site‐closure process. The ability of the technology to remediate soil and groundwater impacted by chlorinated solvents and petroleum hydrocarbons regardless of lithology proves to be beneficial over conventional in situ technologies that are dependent on advective flow. These conventional technologies include: soil vapor recovery, air sparging, and pumpand‐treat, or the delivery of fluids to the subsurface such as chemical oxidization and bioremediation. The technology is very tolerant of subsurface heterogeneities and actually performs as well in low‐permeability silts and clay as in higher‐ permeability sands and gravels. ERH is often implemented around and under buildings and public access areas without upsetting normal business operations. ERH may also be combined with other treatment technologies to optimize and enhance their performance. This article describes how the technology was developed, how it works, and provides two case studies where ERH was used to remediate complex lithologies. © 2005 Wiley Periodicals, Inc.     

1,4‐Dioxane Treatment Technologies

The chlorinated solvent stabilizer 1,4‐dioxane (DX) has become an unexpected and recalcitrant groundwater contaminant at many sites across the United States. Chemical characteristics of DX, such as miscibility and low sorption potential, enable it to migrate at least as far as the chlorinated solvent from which it often originates. This mobility and recalcitrance has challenged remediation professionals to redesign existing treatment systems and monitoring networks to accommodate widespread contamination. Furthermore, remediation technologies commonly applied to chlorinated solvent co‐contaminants, such as extraction and air stripping or in situ enhanced reductive dechlorination, are relatively ineffective on DX removal. These difficulties in treatment have required the industry to identify, develop, and demonstrate new and innovative technologies and approaches for both ex situ and in situ treatment of this emerging contaminant. Great strides have been made over the past decade in the development and testing of remediation technologies for removal or destruction of DX in groundwater. This article briefly summarizes the fate and transport characteristics of DX that make it difficult to treat, and presents technologies that have been demonstrated to be applicable to groundwater treatment at the field scale.  ©2016 Wiley Periodicals, Inc.     

Case Study and Retrospective: Aerobic Fixed Film Biological Treatment Process for 1,4‐Dioxane at the Lowry Landfill Superfund Site

An aerobic fixed film biological treatment system has been successfully treating recovered groundwater/landfill leachate containing 1,4‐dioxane, tetrahydrofuran (THF), and other constituents since 2003. The most likely mode of 1,4‐dioxane biotransformation is via a cometabolic pathway in the presence of THF. Pilot studies conducted during the process development phase established a design basis process loading factor of 0.6 g 1,4‐dioxane and THF (as chemical oxygen demand [COD])/g total solids per day and proved the efficacy of the process. Full‐scale design includes the use of three parallel moving bed bioreactors with effluent recycle capability. Removal efficiencies in excess of 98 percent have been documented for 1,4‐dioxane. Evolving operational challenges are associated with recent trends in 1,4‐dioxane pretreatment discharge limitations in combination with ongoing process optimization and increased influent flow rate conditions associated with seasonal precipitation patterns. ©2016 Wiley Periodicals, Inc.     

Breakthrough in 2D‐CSIA Technology for 1,4‐Dioxane

A dual isotope technology based on compound‐specific stable isotope analysis of carbon and hydrogen (2D‐CSIA) was recently developed to help identify sources and monitor in situ degradation of the contaminant 1,4‐dioxane (1,4‐D) in groundwater. Site investigation and optimized remediation have been the focus of thousands of CSIA applications completed for volatile organic contaminants (VOCs) worldwide. CSIA for the water miscible 1,4‐D, however, has been technically challenging. The most commercially available sample preparation settings “Purge and Trap” for VOC could not efficiently extract 1,4‐D out of water for a reliable CSIA measurement, especially when the concentration is below 100 μg/L. Such a high reporting limit has prevented CSIA from being used for effective site investigation and remediation monitoring at most 1,4‐D contaminated sites, where 1,4‐D is often present at very low ppb levels. This article outlines the recent breakthrough in 2D‐CSIA technology for 1,4‐D in water, reported down to ～1 μg/L for carbon, and ～10 μg/L to 20 μg/L for hydrogen using solid‐phase extraction based on EPA Method 522, and its benefit is highlighted through a case study at a 1,4‐D contaminated site. ©2016 Wiley Periodicals, Inc.     

Combined thermal and zero‐valent iron In Situ soil mixing remediation technology

Thermal remediation of contaminated soils and groundwater by injection of hot air and steam using large‐diameter auger in situ soil mixing effectively remediates volatile and semivolatile organic compounds. This technology removes large amounts of contamination during the early treatment stages, but extended treatment times are needed to achieve high removal percentages. Combining thermal treatment with another technology that can be injected and mixed into the soil, and that continues to operate after removal of the drilling equipment, improves removal efficiency, and reduces cost. Using field‐determined pseudo first‐order removal rates, the cost of the combined remediation of chlorinated volatile organic compounds (CVOCs) by thermal treatment followed by reductive dechlorination by iron powder has been estimated as 57 percent of the cost of thermal treatment alone. This analysis was applied to a case‐study remediation of 48,455 cubic yards, which confirmed the cost estimate of the combined approach and showed over 99.8 percent removal of trichloroethene and other chlorinated VOCs. © 2010 Wiley Periodicals, Inc.     

New advancements for in situ treatment using electrical resistance heating

Electrical resistance heating (ERH) is proving to be an effective technology to rapidly heat the subsurface and, in doing so, removing volatile organic compounds. Practitioners of this technology have observed that other processes (biodegradation, abiotic degradation, hydrolysis, and possibly others) occur to break down the chemicals of concern, and remediation is not solely accomplished through vaporization. Few sites treated using ERH have been monitored during and after treatment to identify and evaluate the processes occurring and assess the contribution of these other biological and chemical processes in the remediation effort so that they may be incorporated in the remediation design. At Fort Lewis, Washington, a landfill has been undergoing ERH treatment in three phases, where chlorinated volatile organic compounds represent the primary chemicals of concern in soil and groundwater. Other chemicals of concern include petroleum products, oils, and lubricants. The Fort Lewis remediation projects provided an opportunity to observe the reactions occurring in the subsurface during ERH and fine‐tune the study with each phase of operation. This study is still under way. However, the data gathered to date, which focuses on biodegradation, provides insights into the processes that have been observed. For the Fort Lewis site, biotic and abiotic degradation processes have been observed throughout the range of operating temperatures. At the lower temperature ranges (up to 70°C), biological processes appear to predominate. Above 70°C, abiotic processes become much more active. The goal of this work is to eventually optimize the use of these intrinsic processes in ERH remediation to reduce energy requirements and costs. © 2007 Wiley Periodicals, Inc.     

Electrical resistance heating of volatile organic compounds in Sedimentary rock

Electrical resistance heating (ERH) has become a common method of remediation for volatile organic compounds (VOCs) in unconsolidated soils, both above and below the water table. Recently, use of ERH has expanded to include treatment of contaminated sedimentary bedrock. This article describes the implementation issues for rock remediation and provides case studies of three sites remediated by ERH in Maryland, New Jersey, and Indiana. With proper design, remediation of bedrock can be as effectively completed as remediation of overburden materials. © 2010 Wiley Periodicals, Inc.     

Electrical Resistance Heating of Volatile Organic Compounds in Sedimentary Rock

Electrical resistance heating (ERH) is a common method of remediation for volatile organic compounds in unconsolidated soils, both above and below the water table. In the past eight years, ERH has been used to successfully treat 10 or more contaminated sedimentary bedrock sites. Sedimentary bedrock treatment has recently expanded to greater depths and into karst limestone environments. This article describes the implementation issues for rock remediation and provides case studies of three sites remediated by ERH in Pennsylvania and Alabama. With proper design, the remediation of sedimentary bedrock can be completed as effectively as the remediation of overburden materials. © 2014 Wiley Periodicals, Inc.     

Evaluation of natural attenuation at a 1,4‐dioxane‐contaminated site

1,4‐Dioxane entered the environment as a result of historic leaks and spills in the production area at an industrial facility in the southeastern coastal plain. The areal extent of the 1,4‐dioxane plume is several hundred acres and is largely contained on the site. Land use adjacent to the plant property is primarily undeveloped (wetlands or woods) or industrial, with a small area of mixed land use (commercial/residential) to the southwest and north. The surficial aquifer is a relatively simple hydrogeologic system with well‐defined boundaries and is comprised of a 50‐ to 70‐foot‐thick deposit of alluvial/fluvial sand and gravel that overlies an aquitard in excess of 100 feet thick. A groundwater flow model, developed and calibrated using field‐measured data, was used for the fate‐and‐transport modeling of 1,4‐dioxane. The flow‐and‐transport model, combined with the evaluation of other site geochemical data, was used to support the selection of monitored natural attenuation (MNA) as the proposed groundwater remedy for the site. Since the active sources of contamination have been removed and the modeling/field data demonstrated that the plume was stable and not expanding, the proposed MNA approach was accepted and approved by the regulatory agency for implementation in 2004. Subsequent accumulated data confirm that concentrations in the 1,4‐dioxane plume are declining as predicted by the fate‐and‐transport modeling. © 2008 Wiley Periodicals, Inc.     

A Multiple Lines of Evidence Framework to Evaluate Intrinsic Biodegradation of 1,4‐Dioxane

Development of a multiple lines of evidence (MLOE) framework to evaluate the intrinsic biodegradation potential of 1,4‐dioxane is vital to implementing management strategies at groundwater sites impacted by 1,4‐dioxane. A comprehensive MLOE approach was formed to provide significant evidence of natural degradation of 1,4‐dioxane comingled with tetrahydrofuran (THF) within a large, diffuse plume. State‐of‐the art molecular biological analyses and compound‐specific isotope analysis (CSIA) were employed to support more traditional approaches for data analysis (concentration trend analyses, spatial distribution, temporal changes, geochemical biodegradation attenuation indicators, plume mass estimates, and fate and transport modeling). The molecular analyses demonstrated that microorganisms capable of both metabolic and cometabolic degradation of 1,4‐dioxane were present throughout the groundwater plume, whereas the CSIA data provided supporting evidence of biodegradation. 1,4‐Dioxane biomarkers were present and abundant throughout the 1,4‐dioxane plume, and our biomarkers tracked the plume with reasonable accuracy. Evidence also suggests that THF‐driven cometabolic biodegradation as well as catabolic 1,4‐dioxane biodegradation were active at this site. These data supplemented the traditional lines of evidence approaches, which demonstrated that 1,4‐dioxane attenuation was occurring across the groundwater plume and that nondestructive physical processes alone did not account for the observed 1,4‐dioxane attenuation. This MLOE framework combining new and traditional analyses demonstrates that this site has a significant capacity for intrinsic biodegradation of 1,4‐dioxane. ©2016 Wiley Periodicals, Inc.     

Innovative applications of subgrade biogeochemical reactors: Three case studies

Subgrade biogeochemical reactors (SBGRs) are an in situ remediation technology shown to be effective in treating contaminant source areas and groundwater hot spots, while being sustainable and economical. This technology has been applied for over a decade to treat chlorinated volatile organic compound source areas where groundwater is shallow (e.g., less than approximately 30 feet below ground surface [ft bgs]). However, this article provides three case studies describing innovative SBGR configurations recently developed and tested that are outside of this norm, which enable use of this technology under more challenging site conditions or for treatment of alternative contaminant classes. The first SBGR case study addresses a site with groundwater deeper than 30 ft bgs and limited space for construction, where an SBGR column configuration reduced the maximum trichloroethene (TCE) groundwater concentration from 9,900 micrograms per liter (μg/L) to <1 μg/L (nondetect) within approximately 15 months. The second SBGR is a recirculating trench configuration that is supporting remediation of a 5.7‐acre TCE plume, which has significant surface footprint constraints due to the presence of endangered species habitat. The third SBGR was constructed with a new amendment mixture and reduced groundwater contaminant concentrations in a petroleum hydrocarbon source area by over 97% within approximately 1 year. Additionally, a summary is provided for new SBGR configurations that are planned for treatment of additional classes of contaminants (e.g., hexavalent chromium, 1,4‐dioxane, dissolved explosives constituents, etc.). A discussion is also provided describing research being conducted to further understand and optimize treatment mechanisms within SBGRs, including a recently developed sampling approach called the aquifer matrix probe.     

Advanced site diagnostic tool 3D‐CSIA for in situ remediation

In situ remediation is inherently considered “green remediation.” The mechanisms of destruction by in situ technologies, however, are often unseen and not well understood. Further, physical effects of amendment application affect concentration data in an identical manner as the desired reactive mechanism. These uncertainties have led to the weight‐of‐evidence approach when proving viability: multiple rounds of data collection, bench studies, pilot studies, and so on. Skipping these steps has resulted in many failed in situ applications. Traditional assessment data are often tangential to the desired information (e.g., “Is contaminant being destroyed or just being pushed around and diluted?” and “What is the mechanism of the destruction and can it be monitored directly?”). An advanced site diagnostic tool, “Three‐Dimensional Compound Specific Stable Isotope Analysis” (3D‐CSIA), can assess the viability of in situ technologies by providing definitive data on contaminant destruction that are not concentration‐related. The 3D‐CSIA tool can also locate source zones and apportion remediation cost by identifying plumes of different isotope signatures and fractionation trends. Further, use of the 3D‐CSIA tool allows remediation professionals to evaluate effectiveness of treatment and make better decisions to expedite site closure and minimize costs. This article outlines the fundamentals of advanced site diagnostic tool 3D‐CSIA in detail, and its benefit is highlighted through a series of case studies at chlorinated solvent–contaminated sites. © 2010 Wiley Periodicals, Inc.     

Rapid full‐scale bioremediation of perchlorate in soil at a large brownfields site

The former Bermite site north of Los Angeles, California, was used to manufacture various explosives and related products containing energetic compounds, including perchlorate. Remediation of perchlorate in site soil and groundwater is being conducted to meet regulatory requirements and allow planned redevelopment activities to proceed. The general approach to perchlorate remediation of shallow soil at the site includes excavation of affected soils followed by ex situ bioremediation. Glycerin was chosen for use as an electron donor because of its stability, safety, low cost, and regulatory acceptance. However, full‐scale bioremediation operation with glycerin initially resulted in inconsistent results despite consistent perchlorate biodegradation observed in treatability study microcosms. To eliminate the inconsistency and optimize the biotreatment process, additional studies were performed in the field on parallel tracks to determine crucial factor(s) that influenced inconsistent breakdown of perchlorate in site soils. Total Kjeldahl nitrogen (TKN) was determined to be a significant factor limiting perchlorate biodegradation. The addition of di‐ammonium phosphate (DAP) resulted in the consistent and complete perchlorate removal, generally within two weeks of incubation with a median destruction rate of about 200 μg/kg/day. Soil processing rates were gradually increased over the year, and, by the summer, approximately 2,000 to 2,500 tons of soil were being processed per day with a total of approximately 160,000 tons processed by the end of July. The total unit treatment cost for the process is about approximately $35/ton. The glycerin‐DAP process is playing a major role in the remediation of this 1,000‐acre former industrial site. © 2008 Wiley Periodicals, Inc.     

Comparing PFAS to other groundwater contaminants: Implications for remediation

Established groundwater contaminants such as chlorinated solvents and hydrocarbons have impacted groundwater at hundreds of thousands of sites around the United States and have been responsible for multibillion dollar remediation expenditures. An important question is whether groundwater remediation for the emerging contaminant class comprised of per‐ and polyfluoroalkyl substances (PFAS) will be a smaller, similar, or a larger‐scale problem than the established groundwater contaminants. A two‐pronged approach was used to evaluate this question in this paper. First, nine quantitative scale‐of‐remediation metrics were used to compare PFAS to four established contaminants: chlorinated solvents, benzene, 1,4‐dioxane, and methyl tert‐butyl ether. These metrics reflected the prevalence of the contaminants in the U.S., attenuation potential, remediation difficulty, and research intensity. Second, several key challenges identified with PFAS remediation were evaluated to see similar situations (qualitative analogs) that have been addressed by the remediation field in the past. The results of the analysis show that four out of nine of the evaluated quantitative metrics (production, number of potential sites, detection frequency, required destruction/removal efficiency) indicate that the scale of PFAS groundwater remediation may be smaller compared to the current scale of remediation for conventional groundwater contaminants. One attenuation metric, median plume length, suggests that overall PFAS remediation could pose a greater challenge compared to hydrocarbon sites, but only slightly larger than chlorinated volatile organic compounds sites. The second attenuation metric, hydrophobic sorption, was not definitive regarding the potential scale of PFAS remediation. The final three metrics (regulatory criteria, in‐situ remediation capability, and research intensity) all indicate that PFAS remediation might end up being a larger scale problem than the established contaminants. An assessment of the evolution of groundwater remediation capabilities for established contaminants identified five qualitative analogs for key PFAS groundwater remediation issues: (a) low‐level detection analytical capabilities; (b) methods to assess the risk of complex chemical mixtures; (c) nonaqueous phase dissolution as an analog for partitioning, precursors, and back diffusion at PFAS sites; (d) predictions of long plume lengths for emerging contaminants; and (e) monitored natural attenuation protocols for other non‐degrading groundwater contaminants. Overall the evaluation of these five analogs provided some comfort that, while remediating the potential universe of PFAS sites will be extremely challenging, the groundwater community has relevant past experience that may prove useful. The quantitative metrics and the qualitative analogs suggest a different combination of remediation approaches may be needed to deal with PFAS sites and may include source control, natural attenuation, in‐situ sequestration, containment, and point‐of‐use treatment. However, as with many chlorinated solvent sites, while complete restoration of PFAS sites may be uncommon, it should be possible to prevent excessive exposure of PFAS to human and ecological receptors.     

Smart Characterization—An Integrated Approach for Evaluating a Complex 1,4‐Dioxane Site

Smart characterization approaches apply the latest high‐resolution site characterization methods to find the contaminant mass flux, by integrating relative permeability mapping, classical hydrostratigraphy interpretation, and high‐density groundwater and saturated soil sampling. The key factor that makes Smart characterization different is the application of quantitative saturated soil sampling in less permeable slow advection and storage zones to diagnose plume maturity and understand its implications for remedy selection and performance. Because direct sensing tools like the membrane interface probe are capable of providing screening‐level assessments for hydrocarbons and chlorinated solvents in storage zones, but not 1,4‐dioxane, the recommended Smart approach involves application of specialized high‐capacity mobile laboratories or rapid turn‐around using fixed commercial labs. In addition to the benefit of rapidly characterizing sites, Smart characterization facilitates a flux‐based conceptual site model, which allows stakeholders to focus remedies on the mobile portion of the contaminant mass or, in effect, the mass that matters. Through systematic planning and implementation, predesign characterization can be completed to optimize source and plume remedy strategies, balancing investment in Smart characterization with reductions in total life‐cycle costs to ensure that an appropriate return on investigation is obtained.  © 2016 Wiley Periodicals, Inc.