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.     

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.     

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.     

Remediation of chlorinated ethenes,ethanes, and methanes in groundwater using carbon‐ and iron‐based electron donor

Field‐scale pilot tests were performed to evaluate enhanced reductive dechlorination (ERD) of dissolved chlorinated solvents at a former manufacturing facility located in western North Carolina (the site). Results of the site assessment indicated the presence of two separate chlorinated solvent–contaminated groundwater plumes, located in the northern and southern portions of the site. The key chlorinated solvents found at the site include 1,1,2,2‐tetrachloroethane, trichloroethene, and chloroform. A special form of EHC^® manufactured by Adventus Americas was used as an electron donor at this site. In this case, EHC is a pH‐buffering electron donor containing controlled release carbon and ZV Iron MicroSphere 200, a micronscale zero‐valent iron (ZVI) manufactured by BASF. Approximately 3,000 pounds of EHC were injected in two Geoprobe^® boreholes in the saprolite zone (southern plume), and 3,500 pounds of EHC were injected at two locations in the partially weathered rock (PWR) zone (northern plume) using hydraulic fracturing techniques. Strong reducing conditions were established immediately after the EHC injection in nearby monitoring wells likely due to the reducing effects of ZV Microsphere 200. After approximately 26 months, the key chlorinated VOCs were reduced over 98 percent in one PWR well. Similarly, the key chlorinated solvent concentrations in the saprolite monitoring wells decreased 86 to 99 percent after initial increases in concentrations of the parent chlorinated solvents. The total organic carbon and metabolic acid concentrations indicated that the electron donor lasted over 26 months after injection in the saprolite aquifer. © 2009 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.     

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.     

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.     

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.     

In Situ treatment of PFAS‐impacted groundwater using colloidal activated Carbon

Poly‐ and perfluoroalkyl substances (PFASs) have been identified by many regulatory agencies as contaminants of concern within the environment. In recent years, regulatory authorities have established a number of health‐based regulatory and evaluation criteria with groundwater PFAS concentrations typically being less than 50 nanograms per liter (ng/L). Subsurface studies suggest that PFAS compounds are recalcitrant and widespread in the environment. Traditionally, impacted groundwater is extracted and treated on the surface using media such as activated carbon and exchange resins. These treatment technologies are generally expensive, inefficient, and can take decades to reach treatment objectives. The application of in situ remedial technologies is common for a wide variety of contaminants of concern such as petroleum hydrocarbons and volatile organic compounds; however, for PFASs, the technology is currently emerging. This study involved the application of colloidal activated carbon at a site in Canada where the PFASs perfluorooctanoate (PFOA) and perfluorooctane sulfonic acid (PFOS) were detected in groundwater at concentrations up to 3,260 ng/L and 1,450 ng/L, respectively. The shallow silty‐sand aquifer was anaerobic with an average linear groundwater velocity of approximately 2.6 meters per day. The colloidal activated carbon was applied using direct‐push technology and PFOA and PFOS concentrations below 30 ng/L were subsequently measured in groundwater samples over an 18‐month period. With the exception of perfluoroundecanoic acid, which was detected at 20 ng/L and perfluorooctanesulfonate which was detected at 40 ng/L after 18 months, all PFASs were below their respective method detection limits in all postinjection samples. Colloidal activated carbon was successfully distributed within the target zone of the impacted aquifer with the activated carbon being measured in cores up to 5 meters from the injection point. This case study suggests that colloidal activated carbon can be successfully applied to address low to moderate concentrations of PFASs within similar shallow anaerobic aquifers.     

Demonstrating the In Situ Biodegradation Potential of Phenol Using Bio‐Sep® Bio‐Traps® and Stable Isotope Probing

The effect of phenol concentration on phenol biodegradation at an industrial site in the south of Wales, United Kingdom, was investigated using standard Bio‐Sep^® Bio‐Traps^® and Bio‐Traps^® coupled with stable isotope probing (SIP). Unlike many ¹³C‐amendments used in SIP studies (such as hydrocarbons) that physically and reversibly adsorb to the activated carbon component of the Bio‐Sep^® beads, phenol is known to irreversibly chemisorb to activated carbon. Bio‐Traps^® were deployed for 32 days in nine site groundwater monitoring wells representing a wide range of phenol concentrations. Bio‐Traps^® amended with ¹³C‐phenol were deployed together with non‐amended Bio‐Traps® in three wells. Quantitative polymerase chain reaction (qPCR) analysis of Bio‐Traps^® post‐deployment indicated an inhibitory effect of increasing phenol concentration on both total eubacteria and aerobic phenol‐utilizing bacteria as represented by the concentration of phenol hydroxylase gene. Despite the chemisorption of phenol to the Bio‐Sep^® beads, activated carbon stable isotope analysis showed incorporation of ¹³C into biomass and dissolved inorganic carbon (DIC) in each SIP Bio‐Trap^® indicating that chemisorbed amendments are bioavailable. However, there was a clear effect of phenol concentration on ¹³C incorporation in both biomass and DIC confirming phenol inhibition. These results suggest that physical reductions of the phenol concentrations in some areas of the plume will be required before biodegradation of phenol can proceed at a reasonable rate. © 2013 Wiley Periodicals, Inc.     

Pilot scale testing composite swellable organosilica nanoscale zero‐valent iron—Iron‐Osorb®—for in situ remediation of trichloroethylene

Iron‐Osorb^® is a solid composite material of swellable organosilica with embedded nanoscale zero‐valent iron that was formulated to extract and dechlorinate solvents in groundwater. The unique feature of the highly porous organosilica is its strong affinity for chlorinated solvents, such as trichloroethylene (TCE), while being impervious to dissolved solids. The swellable matrix is able to release ethane after dechlorination and return to the initial state. Iron‐Osorb^® was determined to be highly effective in reducing TCE concentrations in bench‐scale experiments. The material was tested in a series of three pilot scale tests for in situ remediation of TCE in conjunction with the Ohio Environmental Protection Agency at a site in central Ohio. Results of these tests indicate that TCE levels were reduced for a period of time after injection, then leveled out or bounced back, presumably due to depletion of zero‐valent iron. Use of tracer materials and soil corings indicate that Iron‐Osorb^® traveled distances of at least 20 feet from the injection point during soil augmentation. The material appears to remain in place once the injection fluid is diluted into the surrounding groundwater. Overall, the technology is promising as a remediation method to treat dilute plumes or create diffuse permeable reactive barriers. Keys to future implementation include developing injection mechanisms that optimize soil distribution of the material and making the system long‐lasting to allow for continual treatment of contaminants emanating from the soil matrix. © 2011 Wiley Periodicals, Inc.     

Chlorinated Hydrocarbon–Contaminated Site Investigation With Optimized 3D‐CSIA Approach

An optimized “Three‐Dimensional Compound Specific Isotope Analysis (3D‐CSIA)'' investigation was conducted at a chlorinated hydrocarbon–contaminated site in order to (1) determine if multiple onsite sources of groundwater contamination existed and (2) demonstrate the cost‐effectiveness of applying isotope fingerprinting at such a complex contaminated site. Previous groundwater investigations identified chlorinated hydrocarbons at levels that significantly exceed drinking‐water standards but failed to determine the source(s) of contamination due to the lack of vadose‐zone contamination and the absence of groundwater contaminants in shallow portions of the surficial aquifer. To better understand the contaminant source(s), groundwater samples were taken and tested for both the presence of chlorinated hydrocarbons and their isotopic signatures of ¹³C/¹²C, ³⁷Cl/³⁵Cl, and ²H/¹H. A site investigation with an optimized 3D‐CSIA approach revealed multiple chlorinated hydrocarbon releases from different sources, which was also cost‐effective considering the new lines of evidence of target contaminants obtained with the 3D‐CSIA approach instead of any traditional fingerprinting approaches. In addition, the 3D‐CSIA results inferred in situ bioremediation of chlorinated hydrocarbons would be feasible at the site. © 2013 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.     

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.     

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.     

Optimization and validation of enhanced biological reduction of 1,2,3‐trichloropropane in groundwater

Laboratory and field demonstration studies were conducted to assess the efficacy of enhanced biological reduction of 1,2,3‐trichloropropane (TCP) in groundwater. Laboratory studies evaluated the effects of pH and initial TCP concentrations on TCP reduction and the activity of a microbial inoculum containing Dehalogenimonas (Dhg). Laboratory results showed successful reduction at a pH of 5 to 9 with optimal reduction at 7 to 9 and at initial TCP concentrations ranging from 10 to over 10,000 micrograms per liter (μg/L). Based on findings from the laboratory study, the effects of TCP concentration, geochemical conditions, and amendment concentration on bioremediation efficacy were investigated during a field demonstration at a site with relatively low initial concentrations of TCP (< 2 μg/L). The field demonstration included injection of emulsified vegetable oil (EVO) and lactate as a carbon substrate for biostimulation, followed by bioaugmentation using the microbial inoculum containing Dhg. Post‐injection performance monitoring demonstrated reduction of TCP to below laboratory detection limits (< 0.005 μg/L) after an initial lag period of approximately six months following injections. TCP reduction was accompanied by generation of the degradation byproduct propene. A marginal increase in TCP concentrations, potentially due to an influx of upgradient aerobic groundwater containing TCP, was observed eight months after injections thereby demonstrating the sensitivity of this bioaugmentation application to changes in geochemical parameters. Despite this marginal increase, performance monitoring results indicate continued TCP biodegradation 15 months after implementation of the injection program. This demonstration suggests that enhanced biodegradation of TCP by combining biostimulation and bioaugmentation may be a promising solution to the challenges associated with remediation of TCP, even when present at low part per billion concentrations in groundwater.     

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.     

The in situ treatment of TCE and PFAS in groundwater within a silty sand aquifer

Chlorinated ethenes such as trichloroethene (TCE), cis‐1,2‐dichloroethene (cis‐1,2‐DCE), and vinyl chloride along with per‐ and polyfluoroalkyl substances (PFAS) have been identified as chemicals of concern in groundwater; with many of the compounds being confirmed as being carcinogens or suspected carcinogens. While there are a variety of demonstrated in‐situ technologies for the treatment of chlorinated ethenes, there are limited technologies available to treat PFAS in groundwater. At a former industrial site shallow groundwater was impacted with TCE, cis‐1,2‐DCE, and vinyl chloride at concentrations up to 985, 258, and 54 µg/L, respectively. The groundwater also contained maximum concentrations of the following PFAS: 12,800 ng/L of perfluoropentanoic acid, 3,240 ng/L of perfluorohexanoic acid, 795 ng/L of perfluorobutanoic acid, 950 ng/L of perfluorooctanoic acid, and 2,140 ng/L of perfluorooctanesulfonic acid. Using a combination of adsorption, biotic, and abiotic degradation in situ remedial approaches, the chemicals of concern were targeted for removal from the groundwater with adsorption being utilized for PFAS whereas adsorption, chemical reduction, and anaerobic biodegradation were used for the chlorinated ethenes. Sampling of the groundwater over a 24‐month period indicated that the detected PFAS were treated to either their detection, or below the analytical detection limit over the monitoring period. Postinjection results for TCE, cis‐1,2‐DCE, and vinyl chloride indicated that the concentrations of the three compounds decreased by an order of magnitude within 4 months of injection, with TCE decreasing to below the analytical detection limit over the 24‐month monitoring period. Cis‐1,2‐DCE, and vinyl chloride concentrations decreased by over 99% within 8 months of injections, remaining at or below these concentrations during the 24‐month monitoring period. Analyses of Dehalococcoides, ethene, and acetylene over time suggest that microbiological and reductive dechlorination were occurring in conjunction with adsorption to attenuate the chlorinated ethenes and PFAS within the aquifer. Analysis of soil cores collected pre‐ and post‐injection, indicated that the distribution of the colloidal activated carbon was influenced by small scale heterogeneities within the aquifer. However, all aquifer samples collected within the targeted injection zone contained total organic carbon at concentrations at least one order of magnitude greater than the preinjection total organic carbon concentrations.     

Successful full‐scale enhanced anaerobic dechlorination at a NAPL strength 1,1,1‐TCA source area

Bioremediation of 1,1,1‐trichloroethane (TCA) is more challenging than bioremediation of other chlorinated solvents, such as tetrachloroethene (PCE) and trichloroethene (TCE). TCA transformation often occurs under methanogenic and sulfate‐reducing conditions and is mediated by Dehalobacter. The source area at the project site contains moderately permeable medium sand with a low hydraulic gradient and is approximately 0.5 acre. TCA contamination generally extended to 35 feet, with the highest concentrations at approximately 20 feet. The concentrations then decreased with depth; several wells contained 300 to 600 mg/L of TCA prior to bioremediation. The area of treatment also contained 2 to 30 mg/L of TCE from an upgradient source. Initial site groundwater conditions indicated minimal biotic dechlorination and the presence of up to 20 mg/L of nitrate and 90 mg/L of sulfate. Microcosm testing indicated that TCA dechlorination was inhibited by the site's relatively low pH (5 to 5.5) and high TCA concentration. After the pH was adjusted and TCA concentrations were reduced to less than 35 mg/L (by dilution with site water), dechlorination proceeded rapidly using whey (or slower with sodium lactate) as an electron donor. Throughout the remediation program, increased resistance to TCA inhibition (from 35 to 200 mg/L) was observed as the microbes adapted to the elevated TCA concentrations. The article presents the results of a full‐scale enhanced anaerobic dechlorination recirculation system and the successful efforts to eliminate TCA‐ and pH‐related inhibition. © 2012 Wiley Periodicals, Inc.     

Carbon isotope forensics for methane source identification

Methane (CH₄) in ecosystems originates from ancient petroleum formed deep within the earth and/or via microbial fermentation of organic carbon and subsequent reduction of carbon dioxide (CO₂). Given the complexity of different ecosystems, origins of CH₄ present can be difficult to determine. This issue was realized in a situation where an antimethanogenic in situ chemical reduction (ISCR) remedial amendment containing organic carbon plus zero‐valent iron was applied to treat chlorinated solvents in groundwater at a former dry cleaner facility. The technology rapidly and effectively reduced the concentration of tetrachloroethene in groundwater thus meeting project goals without the stoichiometric accumulation of catabolites such as trichloroethene (TCE), cis‐1,2‐dichloroethene, or vinyl chloride and without excessive methanogenesis (e.g., <2 mg/L) in the treated area. However, approximately 9 months after treatment, increased levels of CH₄ (from 5 to 10 mg/L) were observed downgradient from the treated area. The applied remedial amendment contained approximately 60% (weight basis) fermentation organic carbon and was therefore a potential source of this CH₄. However, there was <500 mg/L total organic carbon in groundwater emanating from the upgradient treatment area which was unlikely sufficient to produce that much CH₄. Moreover, the soil gas also contained benzene, toluene, ethylbenzene, and xylenes and other gasoline constituents. These data suggested that the presence of three gasoline/diesel underground storage tanks that were previously closed in place with no active remediation performed could be the source of elevated CH₄. Thirdly, there were sewer lines, utilities, multiple gasoline stations, and industrial activities in the immediate area. With an initial assumption that CH₄ source(s) could include the ISCR amendment over stimulation of production, gasoline sourced CH₄ from nearby leaking lines, or sewage from local fractured pipes, carbon isotope analyses—radiocarbon (Δ¹⁴C) and stable carbon (δ¹³C)—were coupled with CH₄ and CO₂ concentration data from groundwater samples to determine the origin of respired carbon. The δ¹³C range for carbon sources respired in the process would be approximately ?26.5‰ to ?33.0‰ for the ISCR amendment and total petroleum hydrocarbons (TPH) residuals, respectively. Δ¹⁴C is approximately 0‰ and ?999‰ for the ISCR amendment (young carbon) and TPH (old carbon), respectively. The isotopic signature of respired gasses confirmed that elevated CH₄ downgradient of the treated area originated primarily from sewer gasses (or fermentation of liquids released from sewer lines). This study provides an overview of the capability to apply carbon isotope geochemistry to confirmation of remedial protocols and sources of anthropogenic carbon pools that conclusively identify the origin of CH₄ in a complex ecosystem undergoing a remedial action.