Coupling surfactants/cosolvents with oxidants for enhanced DNAPL removal: A review

Surfactants and cosolvents are useful for enhancing the apparent solubility of dense nonaqueous‐phase liquid (DNAPL) compounds during surfactant‐enhanced aquifer remediation (SEAR). In situ chemical oxidation (ISCO) with permanganate, persulfate, and catalyzed hydrogen peroxide has proven to be a cost‐effective and viable remediation technology for the treatment of a wide range of organic contaminants. Coupling compatible remedial technologies either concurrently or sequentially in a treatment train is an emerging concept for more effective cleanup of DNAPL‐contaminated sites. Surfactants are effective for DNAPL mass removal but not useful for dissolved plume treatment. ISCO is effective for plume control and treatment but can be less effective in areas where large masses of DNAPL are present. Therefore, coupling SEAR with ISCO is a logical next step for source‐zone treatment. This article provides a critical review of peer‐reviewed scientific literature, nonreviewed professional journals, and conference proceedings where surfactants/cosolvents and oxidants have been utilized, either concurrently or sequentially, for DNAPL mass removal. © 2010 Wiley Periodicals, Inc.     

Evaluation of PFAS treatment technology: Alkaline ozonation

A bench‐scale treatability study was performed to evaluate the effectiveness of alkaline ozonation on removing per‐ and polyfluoroalkyl substances (PFAS) present in groundwater at a former industrial site in Michigan. The study involved testing the PFAS‐impacted groundwater under alkaline ozonating conditions under a range of experimental conditions, including modifying pH, hydrogen peroxide‐to‐ozone molar ratio doses, length of ozonation pretreatment times, and sampling techniques. PFAS‐spiked samples were used to determine if inorganic ions such as fluoride (F^?), sulfate (SO₄^2?), formate (HCOO^?), acetate (CH₃COO^?), and trifluoroacetate (CF₃COO^?) were generated or if there were decreases in total organic fluorine resulting from PFAS treatment. The results from all tests indicate that decreases in PFAS concentrations were due to a combination of removal and destructive mechanisms with enhanced removal under acidic pH ozonation pretreatment conditions. Short‐chain PFAS concentrations increased during the experiments followed by an overall decrease in concentration under continuous alkaline ozonation conditions. Reductions in concentrations in perfluorooctane sulfonic acid of 75–97% were observed. Reductions in concentrations were also observed in other PFAS such as 6:2 FTS, PFHxS, PFOA, and PFNA. To our best knowledge, this is the first time that alkaline ozonation has been performed on PFAS‐impacted water while monitoring a larger suite of PFAS analytes in addition to destruction byproducts. Treatment of PFAS under the conditions discussed in this paper suggests that alkaline ozonation may be a viable remediation option for PFAS‐impacted waters.     

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.     

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.     

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.     

Challenges of soil mixing using catalyzed hydrogen peroxide with rotating dual axis blending technology

Although known to be one of the most effective oxidants for treatment of organic contaminants, catalyzed hydrogen peroxide (CHP) is typically not used for soil mixing applications because of health and safety concerns related to vapor generation and very rapid rates of reaction in open excavations. In likely the first large‐scale in situ CHP soil mixing application, an enhanced CHP, modified Fenton's reagent (MFR), was applied during soil mixing at the Kearsarge Metallurgical Superfund Site in New Hampshire. An innovative rotating dual‐axis blender (DAB) technology was used to safely mix the MFR into low‐plasticity silt and clay soils to remediate residual 1,1,1‐trichloroethane (111TCA); 1,1‐dichloroethene (11DCE); and 1,4‐dioxane (14D). It was expected that the aggressive treatment approach using relatively “greener” hydrogen peroxide (HP) chemistry would effectively treat Site contaminants without significant byproduct impacts to groundwater or the adjacent pond. The remediation program was designed to treat approximately 3,000 cubic yards of residual source area soil in situ by aggressively mixing MFR into the soils. The subsurface interval treated was from 7 to 15 feet below ground surface. To accurately track the soil mixing process and MFR addition, the Site was divided into 109 10‐foot square treatment cells that were precisely located, dosed, and mixed using the DAB equipped with an on‐board GPS system. The use of stabilizing agents along with careful calculation of the peroxide dose helped to ensure vapor‐free conditions in the vicinity of the soil mixing operation. Real‐time sampling and monitoring were critical in identifying any posttreatment exceedences of the cleanup goals. This allowed retreatment and supplemental testing to occur without impacting the soil mixing/in situ chemical oxidation (ISCO) schedule. Posttreatment 24‐hr soil samples were collected from 56 random locations after ensuring that the HP had been completely consumed. The posttreatment test results showed that 111TCA and 11DCE concentrations were reduced to nondetect (ND) or below the cleanup goals of 150 μg/kg for 111TCA and 60 μg/kg for 11DCE. Supplemental posttreatment soil samples, collected six months after treatment, showed 100 percent compliance with the soil treatment goals. Groundwater samples collected one year after the MFR soil mixing treatment program showed either ND or low concentrations for 111TCA, 11DCE, and 14D. Successful stabilization and site restoration was performed after overcoming considerable challenges associated with loss of soil structure, high liquid content, and reduced bearing capacity of the blended soils.     

Integrating total oxidizable precursor assay data to evaluate fate and transport of PFASs

Fate and transport of per‐ and polyfluoroalkyl substances (PFASs) are complex and are not well understood. Among this class of emerging contaminants, perfluoroalkyl acids (PFAAs) comprising perfluoroalkyl carboxylates (PFCAs) and perfluoroalkyl sulfonates (PFSAs) are being studied more frequently than polyfluorinated compounds. PFAAs are persistent in the environment, recalcitrant to biological degradation, and, therefore, widespread. Previous studies have indicated that some PFASs bioaccumulate. The fate and transport of PFAAs can be complicated by the presence of PFAA precursors. The PFAA precursors are defined in this article as those fluorinated chemicals that can be potentially transformed abiotically or biotically into terminal PFCA or PFSA products. Due to potential biotransformation in the environment, PFAA precursors can influence the temporal and lateral distribution of PFAAs in the environment. Presently, only a very small number of PFAA precursors can be quantitatively analyzed by commercial laboratories. For instance, N‐ethyl perfluorooctanesulfonamidoacetic acid and N‐methyl perfluorooctanesulfonamidoacetic acid are the only two precursors included in the most commonly applied PFAS analytical method, U.S. Environmental Protection Agency Method 537. The current commercial laboratory methodologies primarily quantify between 14 and 31 PFASs. As an alternative, a total oxidizable precursor assay (TOPA) was developed to quantify the measurable PFSA and PFCA concentrations after aggressive oxidation converting PFAA precursors abiotically into PFCAs. The difference between PFAA concentrations before and after oxidation can be used to estimate the amount of oxidizable PFAA precursors in the sample. This is one of the first articles that utilized TOPA data to help interpret PFAS fate and transport in the environment.     

TCE plume remediation via ISCR‐enhanced bioremediation utilizing EHC® and KB‐1®

Groundwater below an operating manufacturing facility in Portland, Oregon, was impacted by chlorinated volatile organic compounds (CVOCs), with concentrations indicative of a dense, nonaqueous‐phase liquid (DNAPL) release. The downgradient plume stretched under the adjacent Willamette River, intersecting zones of legacy impacts from a former manufactured gas plant (MGP). An evaluation of source‐area and downgradient plume treatment remedies identified in situ bioremediation as most likely to be effective for the CVOC plume, while leaving the legacy impacts for other responsible parties. With multiple commercially available products to choose from, the team developed and implemented a bench test to identify the most appropriate technology, which was further evaluated in a field pilot study. The results of the testing demonstrated conclusively that bioremediation enhanced by in situ chemical reduction (ISCR) using EHC® and KB‐1® was most appropriate for this site, providing outstanding results. The following describes the implementation and results of the tests. © 2008 Wiley Periodicals, Inc.     

Iron‐mediated abiotic degradation of RDX in a contaminated aquifer

The influence of aqueous‐ and mineral‐phase iron on royal demolition explosive (RDX) destruction has been previously investigated in theoretical settings and bench‐scale tests by various practitioners. The feasible use of in situ redox manipulation to create reactive Fe(II) is contingent upon the aquifer containing enough iron oxides and iron‐bearing clay minerals for the treated zone to remain effective. The following is a summary of a bench‐scale assessment of this relationship using aquifer material from an ongoing groundwater remediation effort at the Iowa Army Ammunition Plant (IAAP). A bench‐scale study was designed to determine the relative contributions of the biotic and iron‐mediated abiotic degradation processes to the net decrease in RDX observed at the site using saturated aquifer samples collected from within the RDX plume. Sterilized samples with a sufficient stoichiometric excess of both soluble and mineral‐phase iron reduced concentrations of RDX in both the soil and water fractions to the same extent as the samples containing native biota. These results indicate that in situ, abiotic degradation of RDX is feasible in areas unsuitable to biotic degradation processes, yielding an additional alternative for in situ RDX remediation. © 2012 Wiley Periodicals, Inc.     

Bench-scale testing of a novel soil PFAS treatment train for informed remedial planning and decision-making

Bench-scale batch tests were conducted to assess the potential applicability of a combined separation/concentration/destruction treatment train to address soils and sediments impacted by per- and polyfluoroalkyl substances (PFAS) contamination at Schriever Space Force Base with historic aqueous film-forming foam (AFFF). Specifically, a novel treatment train coupling soil washing (for treatment of impacted soil/sediment) with foam fractionation (for treatment of the wash water [WW] generated during soil washing) and electrochemical oxidation (ECO, for treatment of the foam fractionate generated during foam fractionation) was evaluated at the bench scale using site-specific materials. Results presented herein show that the AFFF-impacted sandy soils with low organic content were amenable to treatment via soil washing. However, the removal of hydrophobic PFAS, such as perfluorooctanesulfonic acid (PFOS), from the organic-rich sediments was challenging. Results from batch desorption experiments were within a factor of 2 of those generated by soil washing bench studies, suggesting that simple batch tests can potentially be used to reasonably predict the treatment efficacy of soil washing. Long-chained perfluoroalkyl acids (PFAAs) within the WW were removed more effectively in the foam fractionation studies as compared to short-chain PFAAs. Addition of a surfactant, such as cetrimonium bromide (CTAB), enhanced foaming but only marginally improved the treatment of short-chained PFAAs and in some cases inhibited PFOS removal. ECO reduced PFAS concentrations in the foam fractionate generated during foam fractionation by several orders of magnitude. However, generation of unwanted byproducts may warrant further treatment and/or disposal. Overall, results from this study provide a novel data set highlighting the site-dependent nature of these PFAS remedial technologies and how simple, low-cost bench tests can be reliably leveraged for informed decision-making during PFAS remedial planning.     

Biochemical Treatment of Hydraulically Complex Hexavalent Chromium and Chlorinated Volatile Organic Plumes

Groundwater contaminated with hexavalent chromium (Cr⁺⁶) and chlorinated volatile organic compounds (cVOCs) presents unique in situ remedial challenges in an oxygen‐rich environment. On one hand, chemical oxidation would be effective in treating the cVOCs; however, it would not be appropriate to treat Cr⁺⁶. Biological treatment may be appropriate to treat the Cr⁺⁶; however, the cVOC degradation pathway within these mixed plumes is currently following an abiotic pathway with little to no daughter‐product production. Thus, a blended approach was needed to treat both constituents in situ in an effort to avoid a long‐term, costly pump‐and‐treat solution. This article evaluates an in situ biogeochemical stabilization/reduction strategy by injecting an inorganic carbon‐based remedial additive into the geologic and hydrogeologic environment to decrease concentrations within the commingled Cr⁺⁶ and cVOC plume. The concept involves creating favorable redox reducing conditions to shift the groundwater geochemical equilibrium from the more toxic Cr⁺⁶ to the less toxic trivalent chromium (Cr⁺³), with the final outcome being a conversion to chrome oxide that molecularly fixes to the soil grains. In addition, reducing conditions developed for chromium reduction should result in an increase in the available natural formation iron that should further enhance the natural abiotic reduction of cVOCs. © 2013 Wiley Periodicals, Inc.     

Sustainable soil remediation by refrigerated condensation at sites with “high‐concentration” recalcitrant compounds and NAPL: Two case studies

Remediation of recalcitrant compounds at sites with high concentrations of volatile organic compounds (VOCs) or nonaqueous‐phase liquids (NAPLs) can present significant technical and financial (long‐term) risk for stakeholders. Until recently, however, sustainability has not been included as a significant factor to be considered in the feasibility and risk evaluation for remediation technologies. The authors present a framework for which sustainability can be incorporated into the remediation selection criteria focusing specifically on off‐gas treatment selection for soil vapor extraction (SVE) remediation technology. SVE is generally considered an old and standard approach to in situ remediation of soils at a contaminated site. The focus on off‐gas treatment technology selection in this article allows for more in‐depth analysis of the feasibility evaluation process and how sustainable practices might influence the process. SVE is more commonly employed for recovery of VOCs from soils than other technologies and generally employs granular activated carbon (GAC), catalytic, or thermal oxidation, or an emerging alternative technology known as cryogenic‐compression and condensation combined with regenerative adsorption (C3–Technology). Of particular challenge to the off‐gas treatment selection process is the potential variety of chemical constituents and concentrations changing over time. Guidance is available regarding selection of off‐gas treatment technology (Air Force Center for Environmental Excellence, 1996; U.S. Environmental Protection Agency, 2006). However, there are common shortcomings of off‐gas treatment technology guidance and applications; practitioners have rarely considered sustainability and environmental impact of off‐gas treatment technology selection. This evaluation includes consideration of environmental sustainability in the selection of off‐gas treatment technologies and a region‐specific (Los Angeles, California) cost per pound and time of remediation comparisons between GAC, thermal oxidation, and C3–Technology. © 2008 Wiley Periodicals, Inc.     

Selecting state-of-the-art incinerators for complex aqueous wastes

The Rocky Mountain Arsenal (RMA) in Adams County, Colorado has been identified as a priority site on the Superfund National Priority List. The Program Manager's Office of RMA announced in early 1990 its intention to implement installation of a state-of-the-art incineration plant to treat the most complex and controversial waste stream on the site. Established in 1942, RMA served as an Army manufacturing center for chemical agents such as mustard gas, white phosphorus, napalm, and GB nerve agent. Parts of the site were also leased to Shell Oil Company, which manufactured pesticides and other agricultural chemicals at this location between 1952 and 1982. To support these activities, the Army operated a ninety-three-acre surface impoundment called Basin F for collection and evaporation of chemical wastewaters. As a result of the wide variety of wastes received and concentrated at Basin F and early treatment attempts, its contents became one of the most unusual chemical cocktails known to man. By the time a formal interim response action for remediation was initiated in 1985, the composition of the Basin consisted of a multi-phase fluid and sludge, including super-saturated levels of inorganic salts; 30 percent or more organics such as pesticides, military agent by-products, degradation products, and solvents; high levels of ammonia compounds and bound nitrogen; and percent levels of copper, arsenic, and other metals. Selection of a remedial alternative involved twelve years of characterizationstudies and eleven years of treatability testing programs encompassing the universe of containment; encapsulation; stabilization; component separation; and thermal, electrical, chemical, and biological degradation technologies. The program resulted in the selection of a state-of-the-art down-fired liquid incinerator for destruction of aqueous organic contaminants in metallic salt matrices. The treatability demonstration, and the technical justification for selection of the T-Thermal submerged quench incinerator for this application, is the subject of this article.     

Surfactant‐Oxidant Co‐Application for Soil and Groundwater Remediation

In situ chemical oxidation (ISCO) typically delivers oxidant solutions into the subsurface for contaminant destruction. Contaminants available to the oxidants, however, are limited by the mass transfer of hydrophobic contaminants into the aqueous phase. ISCO treatments therefore often leave sites with temporarily clean groundwater which is subject to contaminant rebound when sorbed and free phase contaminants leach back into the aqueous phase. Surfactant Enhanced In situ Chemical Oxidation (S‐ISCO^®) uses a combined oxidant‐surfactant solution to provide optimized contaminant delivery to the oxidants for destruction via desorption and emulsification of the contaminants by the surfactants. This article provides an overview of S‐ISCO technology, followed by an implementation case study at a coal tar contaminated site in Queens, New York. Included are data points from the site which demonstrate how S‐ISCO delivers desorbed contaminants without uncontrolled contaminant mobilization, as desorbed and emulsified contaminants are immediately available to the simultaneously injected oxidant for reaction. ©2016 Wiley Periodicals, Inc.     

Six pilot‐scale studies evaluating the in situ treatment of PFAS in groundwater

Per‐ and polyfluoroalkyl substances (PFAS) have been identified by many regulatory agencies as emerging contaminants of concern in a variety of media including groundwater. Currently, there are limited technologies available to treat PFAS in groundwater with the most frequently applied approach being extraction (i.e., pump and treat). While this approach can be effective in containing PFAS plumes, previous studies of pump and treat programs have met with limited remedial success. In situ treatment studies of PFAS have been limited to laboratory and a few field studies. Six pilot‐scale field studies were conducted in an unconfined sand aquifer coimpacted by petroleum hydrocarbon along with PFAS to determine if a variety of reagents could be used to attenuate dissolved phase PFAS in the presence of petroleum hydrocarbons. The six reagents consisted of two chemical oxidants, hydrogen peroxide (H₂O₂) and sodium persulfate (Na₂S₂O₈), and four adsorbents, powdered activated carbon (PAC), colloidal activated carbon (CAC), ion‐exchange resin (IER), and biochar. The reagents were injected using direct push technology in six permeable reactive zone (PRZ) configurations. Groundwater concentrations of various PFAS entering the PRZs ranged up to 24,000 µg/L perfluoropentanoic acid, up to 6,200 µg/L pentafluorobenzoic acid, up to 16,100 µg/L perfluorohexanoic acid, up to 6,080 µg/L perfluoroheptanoic acid, up to 450 µg/L perfluorooctanoic acid, and up to 140 µg/L perfluorononanoic acid. Performance groundwater sampling within and downgradient of the PRZs occurred for up to 18 months using single and multilevel monitoring wells. Results of groundwater sampling indicated that the PFAS were not treated by either the persulfate nor the peroxide and, in some cases, the PFAS increased in concentration immediately following the injection of peroxide and persulfate. Concentrations of PFAS in groundwater sampled within the PAC, CAC, IER, and biochar PRZs immediately after the injection were determined to be less than the method detection limits. Analyses of groundwater samples over the 18‐month monitoring period, indicated that all the PRZs exhibited partial or complete breakthrough of the PFAS over the 18‐month monitoring period, except for the CAC PRZ which showed no PFAS breakthrough. Analysis of cores for the CAC, PAC, and biochar PRZs suggested that the CAC was uniformly distributed within the target injection zone, whereas the PAC and biochar showed preferential injection into a thin coarse‐sand seam. Similarly, analysis of the sand packs of monitoring wells installed before the injection of the CAC, PAC, and biochar indicated that the sand packs of the PAC and biochar preferentially accumulated the reagents compared with the reagent concentrations within the surrounding aquifer by up to 18 times.     

Bioremediation of contaminated soil and sediment by composting

There are many well‐established bioremediation technologies applied commercially at contaminated sites. One such technology is the use of compost material. Composting matrices and composts are rich sources of microorganisms, which can degrade contaminants to innocuous compounds such as carbon dioxide and water. In this article, composting of contaminated soil and sediment was performed on a laboratory bench‐scale pile. Fertilizer was added to increase the nutrient content, and the addition of commercial compost provided a rich source of microorganisms. After maintaining proper composting conditions, the feasibility of composting was assessed by monitoring pH, total volatile solids, total microbial count, temperature, and organic contaminant concentration. The entire composting process occurred over a period of five weeks and resulted in the degradation of contaminants and production of compost with a high nutritional content that could be further used as inocula for the treatment of hazardous waste sites. © 2006 Wiley Periodicals, Inc.     

Ion exchange resin for PFAS removal and pilot test comparison to GAC

Amec Foster Wheeler and Emerging Compounds Treatment Technologies, Inc. tested pilot‐scale ex situ treatment technologies for treatment of poly‐ and perfluorinated alkyl substances (PFAS) in groundwater. The pilot test compared ion exchange resin to granular activated carbon (GAC) and evaluated in‐place regeneration of the resin to restore PFAS removal capacity. During the pilot test, both resin and GAC removed perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) below U.S. Environmental Protection Agency (USEPA) health advisories (HAs) of 0.070 micrograms per liter (μg/L) combined. Compared at a common empty bed contact time (EBCT) of five minutes, the resin treated over eight times as many bed volumes (BVs) of groundwater as GAC before PFOS exceeded the USEPA HA and six times as many BVs for PFOA. On a mass‐to‐mass basis, resin removed over four times as much total PFAS per gram as GAC before breakthrough was observed at the USEPA HA. A solution of organic solvent and brine was used to regenerate the resin in the lead vessel, which had treated water up to the point of PFOS and PFOA breakthrough exceeding the USEPA HAs. The pilot test demonstrated successful in‐place regeneration of the resin to near‐virgin conditions. The regenerated resin was then used to treat the contaminated groundwater up to the same breakthrough point. Compared to the virgin resin loading cycles, PFAS removal results for the regenerated resin were consistent with virgin resin.     

Perfluoroalkyl and polyfluoroalkyl substances thermal desorption evaluation

Per‐ and polyfluoroalkyl substances (PFAS) are highly resistant to biotic and abiotic degradation and can withstand very high temperatures before breaking down. The storage of PFAS‐impacted water and sediments in a holding pond or stockpiled investigation or remedial action‐derived waste is occurring on an increasing number of sites. The most common PFAS water treatment options include granular‐activated carbon and resins and the most common soil treatment options have been primarily limited to excavation, offsite incineration, and, in some cases, soil stabilization. An increasing number of states across the United States are establishing part per trillion PFAS guidance levels for drinking water. Removing PFAS from soils removes PFAS source impacts to groundwater. In this study, volatilization of PFAS from soil treated using in situ thermal heating is evaluated as a treatment method to achieve a high degree of PFAS removal from soils. The evaluation of temperatures needed to achieve removal is described. To minimize vapor treatment required for PFAS thermal remediation, a scrubber was incorporated into the treatment train to transfer PFAS to the liquid phase in a concentrated, low‐volume solution. Vapor‐liquid equilibrium behavior and the extent of PFAS volatilization from impacted soil over a range of temperatures were evaluated. Results showed that heating soil to 350°C and 400°C reduces PFAS soil concentrations by 99.91% and 99.998%, respectively. It was also confirmed that sulfonate‐based PFAS generally required higher temperatures for volatilization to occur than carboxylate‐based PFAS.     

Characterization and pilot‐scale studies for chemical oxidation remediation of fractured shale

The distribution of volatile organic compounds (VOCs) in fractured shale overlain by thin (< 10 feet) overburden at the Watervliet Arsenal near Albany, New York, was initially determined by sampling water from the fracture network using packer systems in boreholes and also using conventional monitoring wells. Furthermore, short‐term pumping and injection tests were conducted and the boreholes were logged using a variety of geophysical and hydrophysical tools. Tetrachloroethene is the dominant VOC in the groundwater, with lesser concentrations of trichloroethene and degradation products (cis‐1,2‐dichloroethene, trans‐1,2‐dichloroethene, and vinyl chloride). The vertical VOC distributions in the rock matrix were obtained from continuous‐cored holes from which small rock samples, collected at many depths between 18 and 150 feet below ground surface, were analyzed. The rock core VOC concentrations were determined by methanol extraction of crushed rock followed by direct methanol injection onto a gas chromatograph and subsequent estimation of rock porewater VOC concentrations. The rock core data support the concept that diffusion‐driven mass transfer has caused nearly all the VOC mass initially present in the fractures to now reside in the rock matrix, which has a porosity three or four orders of magnitude larger than the bulk fracture porosity. The results of the site characterization indicate that an effective site investigation strategy in fractured shale must include characterization of both the fracture and matrix contaminant distribution. These results also indicate that the most favorable remediation technologies for this fractured shale are those that will destroy VOCs in the rock matrix, particularly contaminants in the sorbed phase, and also destroy the VOC mass in the fractures including both dissolved and immiscible phases. The site characterization resulted in the selection of potassium permanganate for an in situ chemical oxidation pilot study. © 2004 Wiley Periodicals, Inc.     

Bench‐ and pilot‐scale applications of electrochemical peroxidation: A new remedial concept

Electrochemical peroxidation (ECP) is a proprietary process that utilizes sacrificial iron electrodes and stochiometrically balanced applications of hydrogen peroxide to efficiently destroy aqueous phase contaminants. In laboratory trials it has been successful in reducing, often to non‐detectable levels, BTEX, fuel additives, chlorinated solvents, and polychlorinated biphenyls in ground waters. The process has also been found effective in reducing the chemical and biological oxygen demand of industrial waste water. Agency‐approved pilot tests will be conducted at two gasoline spill sites during 2000 where traditional pump and treat methods have proven ineffectual because of ground water chemistry or subsurface hydrologic conditions. The ECP process utilizes a tripartite treatment strategy consisting of 1) ex situ chemical oxidation; 2) in situ oxidation by reinjection of treated water with residual oxidants at the head of the plume; and 3) reestablishment of aerobic biodegradation by alteration of subsurface redox conditions. In contrast to other in situ oxidation treatment methods, dissolved iron is derived electrochemically, negating the need for ferrous salt addition. Dilute hydrogen peroxide (3 percent) is incrementally added to maximize oxidation efficiency and eliminate safety and environmental concerns accompanying the use of highly concentrated solutions. Results of laboratory trials and the geological and geochemical considerations of upcoming pilot‐scale applications are presented. Other potential applications currently under investigation include combination with other remedial processes (e.g. permeable barriers and hydrogen release compounds) to insure complete and rapid contaminant mineralization.