Practical Perspectives of 1,4‐Dioxane Investigation and Remediation

1,4‐Dioxane (dioxane) is a contaminant of emerging concern that is classified by the U.S. Environmental Protection Agency as a likely human carcinogen. Dioxane has been used as a minor or major ingredient in many applications, and is also generated as an unwanted by‐product of industrial processes associated with the manufacturing of polyethylene, nonionic surfactants, and many consumer products (cosmetics, laundry detergents, shampoos, etc.). Dioxane is also a known stabilizer of chlorinated solvents, particularly 1,1,1‐trichloroethane, and has been commonly found comingled with chlorinated solvent plumes. Dioxane plumes at chlorinated solvent sites can complicate site closure strategies, which to date have not typically focused on dioxane. Aggressive treatment technologies have greatly advanced and are clearly capable of achieving lower parts per billion cleanup criteria using ex situ advanced oxidation processes and sorption media. In situ chemical oxidation has also been demonstrated to effectively remediate dioxane and chlorinated solvents. Other in situ remedies, such as enhanced bioremediation, phytoremediation, and monitored natural attenuation, have been studied; however, their ability to achieve cleanup levels is still somewhat questionable and is limited by co‐occurring contaminants. This article summarizes and provides practical perspectives on dioxane analysis, plume stability relative to other contaminants, and the development of investigation tools and treatment technologies.     

In Situ Remediation of 1,4‐Dioxane Using Electrical Resistance Heating

Recent regulatory changes need more challenging treatment goals for 1,4‐dioxane. However, significant treatment limitations exist in part due to the high solubility and low Henry's law constant of 1,4‐dioxane. Two case studies are reported with substantial 1,4‐dioxane concentration reductions through in situ thermal remediation via electrical resistance heating (ERH). Concentration reductions greater than 99.8 percent of 1,4‐dioxane have been observed in the field using ERH. Concentrations of 1,4‐dioxane in air and steam extracted by an ERH vapor recovery system have also been evaluated. Laboratory studies were conducted to further understand the mechanisms that enable ERH remediation of 1,4‐dioxane. Vapor liquid equilibrium studies in water and soil were conducted and utilized to develop an ERH treatment cost model for 1,4‐dioxane. Existing field data were correlated to the 1,4‐dioxane treatment cost model. Field observations and laboratory testing indicate steam stripping that occurs through ERH remediation is an effective treatment method for 1,4‐dioxane. ©2015 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.     

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.     

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.     

Synthetic Media: A Promising New Treatment Technology for 1,4‐Dioxane

1,4‐Dioxane (14DX) is classified as a probable human carcinogen by the US Environmental Protection Agency (EPA), and it has toxic effects on the kidney and liver. EPA's Health Advisory Level (HAL) for 14DX is 0.35 micrograms per liter (μg/L). Accordingly, several states have lowered their drinking water advisory levels and site cleanup levels. The widespread occurrence of 14DX in contaminated groundwater has contributed to a growing demand for remediation services. Treating 14DX is a challenge due to its very low Henry's law constant, low sorption potential, and strong ether linkages. The primary solution for 14DX remediation has been various forms of advanced oxidation processes (AOP), namely pump and treat followed by ex situ treatment with catalyzed ultraviolet light oxidation or ozone‐peroxidation. Many of the available advanced oxidation systems are complex, requiring careful monitoring and maintenance to adjust for variable source water and operating conditions. Synthetic media is a relatively new 14DX treatment technology that overcomes many of the operating challenges faced by existing technologies. AMBERSORB? 560 (AMBERSORB) has recently demonstrated the effective removal of 14DX over a wide range of concentrations and operating conditions, including those created by in situ thermal remediation. Consistent and reliable treatment down to sub‐0.3 μg/L levels differentiates synthetic media technology from other 14DX treatment technologies. AMBERSORB provides a solution to the problem of “stranded capital” by offering a 14DX treatment system capable of meeting regulatory standards today and in the foreseeable future. © 2014 Wiley Periodicals, Inc.     

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.     

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.     

Treatment technologies for 1,4‐Dioxane: Fundamentals and field applications

1,4‐Dioxane is a synthetic industrial chemical frequently found at contaminated sites where 1,1,1‐trichloroethane was used for degreasing. It is a probable human carcinogen and has been found in groundwater at sites throughout the United States. The physical and chemical properties and behavior of 1,4‐dioxane create challenges for its characterization and treatment. It is highly mobile and has not been shown to readily biodegrade in the environment. In December 2006, the U.S. Environmental Protection Agency's Office of Superfund Remediation and Technology Innovation (OSRTI) prepared a report titled “Treatment Technologies for 1,4‐Dioxane: Fundamentals and Field Applications.” The report provides information about the chemistry of dioxane, cleanup goals, analytical methods, available treatment technologies, and site‐specific treatment performance data. The information may be useful to project managers, technology providers, consulting engineers, and members of academia faced with addressing dioxane at cleanup sites or in drinking water supplies. This article provides a synopsis of the US EPA report, which is available at http://cluin.org/542R06009 . © 2007 Wiley Periodicals, Inc.