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.     

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 application of colloidal activated carbon for PFAS-contaminated soil and groundwater: A Swedish case study

Soil and groundwater contamination by per- and polyfluoroalkyl substances (PFAS) has been a significant concern to human health and environmental quality. Remediation of contaminated sites is crucial to prevent plume expansion but can prove challenging due to the persistent nature of PFAS combined with their high aqueous mobility. In this case study, we investigated the potential of colloidal activated carbon (CAC) for soil stabilization at the pilot scale, aiming to entrap PFAS and prevent their leaching from soil into groundwater. Monitoring of the site revealed the presence of two potential sources of PFAS contamination at concentrations up to 23 μg L⁻¹ for ∑₁₁PFAS in groundwater. After CAC application, initial results indicated a 76% reduction of ∑₁₁PFAS and high removal rates for long-chain PFAS, such as perfluorooctane sulfonic acid and perfluorooctanoic acid. A spike in concentrations was noticed 6 months after injection of CAC, showing a rebound of the plume and a reduction of treatment effectiveness. Based on long-term monitoring data, the treatment effectiveness for ∑₁₁PFAS dropped to 52%. The rebound of concentrations was attributed to the plume bypass of the barrier due to the presence of high conductivity zones, which likely occurred because of seasonal changes in groundwater flow directions or the CAC application at the site. This demonstrates the need for a detailed and accurate hydrogeological understanding of contaminated sites before designing and applying stabilization techniques, especially at sites with high geologic and hydrologic complexity. The results herein can serve as a guideline for treating similar sites and help avoid potential pitfalls of remedial efforts.     

Water quality impacts on sorbent efficacy for per- and polyfluoroalkyl substances treatment of groundwater

Per- and polyfluoroalkyl substances (PFAS) are a large group of synthetic compounds that have emerged as chemicals of concern in drinking water and groundwater. Typically, such waters are treated to remove PFAS by passing the water through a bed of sorbent material (e.g., activated carbon and anion exchange resins [AIX]). However, the efficacy of these sorbents varies depending on the types and concentrations of PFAS, in addition to water quality conditions such as organic matter content and conductivity (ionic strength). The choice of sorbent material to effectively treat PFAS in complex natural waters will, therefore, depend upon site water quality and PFAS conditions. To help inform these decisions, a series of evaluations using a rapid small-scale column test approach was conducted with two sorbent materials (a granulated activated carbon [GAC] and an AIX), individually and combined, under conditions where conductivity, pH, and organic carbon concentrations were varied in a semifactorial approach. Artificial groundwater batches were prepared to meet these test conditions and spiked with six PFAS compounds (perfluorobutane sulfonic acid [PFBS], perfluorobutanoic acid [PFBA], perfluorohexane sulfonic acid [PFHxS], perfluorohexanoic acid [PFHxA], perfluorooctane sulfonic acid [PFOS], and perfluorooctanoic acid [PFOA]), passed through small columns packed with ground sorbent material for ∼30,000 bed volumes of water for single sorbent treatments and ∼20,000 bed volumes for combined sorbent treatments, during which samples of effluent were captured and analyzed to quantify breakthrough of PFAS from the sorbent materials over time. AIX was found to be more effective than GAC at removing the tested perfluoroalkyl sulfonic acids (PFBS, PFHxS, and PFOS), but GAC was similarly or more effective than AIX at removing perfluorocarboxylic acids (PFBA, PFHxA, and PFOA) under high conductivity conditions. Overall, the efficacy of AIX at removing PFAS was more strongly impacted by organic carbon and conductivity than GAC, while pH had less of an effect on either sorbent's efficacy compared to the other test conditions.     

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.     

Treatment of Perchlorate‐Contaminated Groundwater Using Highly Selective,Regenerable Ion‐Exchange Technology: A Pilot‐Scale Demonstration

Treatment of perchlorate‐contaminated groundwater using highly selective, regenerable ion‐exchange technology has been recently demonstrated at Edwards Air Force Base, California. At an influent concentration of about 450 μg/l ClO₄^?, the bifunctional anion‐exchange resin bed treated approximately 40,000 empty bed volumes of groundwater before a significant breakthrough of ClO₄^? occurred. The presence of relatively high concentrations of chloride and sulfate in site groundwater did not appear to affect the ability of the bifunctional resin to remove ClO₄^?. The spent resin bed was successfully regenerated using the FeCl₃^?HCl regeneration technique recently developed at the Oak Ridge National Laboratory, and nearly 100 percent of sorbed ClO₄^? was displaced or recovered after elution with as little as about two bed volumes of the regenerant solution. In addition, a new methodology was developed to completely destroy ClO₄^? in the FeCl₃^?HCl solution so that the disposal of perchlorate‐containing hazardous wastes could be eliminated. It is therefore anticipated that these treatment and regeneration technologies may offer an efficient and cost‐effective means to remove ClO₄^? from contaminated groundwater with significantly reduced generation of waste requiring disposal. © 2002 Wiley Periodicals, Inc.     

The Hidden Potential of Mass‐based Treatment: A Method for Preventing Rebound

A major challenge for in situ treatment is rebound. Rebound is the return of contaminant concentrations to near original levels following treatment, and frequently occurs because much of the residual nonaqueous phase liquid (NAPL) trapped within the soil capillaries or rock fractures remains unreachable by conventional in situ treatment. Fine‐textured strata have an especially strong capacity to absorb and retain contaminants. Through matrix diffusion, the contaminants dissolve back into groundwater and return with concentrations that can approach pretreatment levels. The residual NAPL then serves as a continuing source of contamination that may persist for decades or longer. A 0.73‐acre (0.3‐hectare) site in New York City housed a manufacturer of roofing materials for approximately 60 years. Coal tar served as waterproofing material in the manufacturing process and releases left behind residual NAPL in soils. An estimated 47,000 pounds (21,360 kg) of residual coal tar NAPL contaminated soils and groundwater. The soils contained strata composed of sands, silty sands, and silty clay. A single treatment using the RemMetrik^® process and Pressure Pulse Technology^® (PPT) targeted the contaminant mass and delivered alkaline‐activated sodium persulfate to the NAPL at the pore‐scale level via in situ treatment. Posttreatment soil sampling demonstrated contaminant mass reductions over 90 percent. Reductions in posttreatment median groundwater concentrations ranged from 49 percent for toluene to 92 percent for xylenes. Benzene decreased by 87 percent, ethylbenzene by 90 percent, naphthalene by 80 percent, and total BTEX by 91 percent. Mass flux analysis three years following treatment shows sustained reductions in BTEX and naphthalene, and no rebound. ©2015 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.     

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.     

Remedial options for chlorinated volatile organics in a partially anaerobic aquifer

A laboratory study was conducted for the selection of appropriate remedial technologies for a partially anaerobic aquifer contaminated with chlorinated volatile organics (VOCs). Evaluation of in situ bioremediation demonstrated that the addition of electron donors to anaerobic microcosms enhanced biological reductive dechlorination of tetrachloroethene (PCE), trichloroethene (TCE), and 1,1,1‐trichloroethane (1,1,1‐TCA) with half‐lives of 20, 22, and 41 days, respectively. Nearly complete reductions of PCE, TCE, 1,1,1‐TCA, and the derivative cis‐dichloroethene were accompanied by a corresponding increase in chloride concentrations. Accumulation of vinyl chloride, ethene, and ethane was not observed; however, elevated levels of ¹⁴CO₂ (from ¹⁴C‐TCE spiked) were recovered, indicating the occurrence of anaerobic oxidation. In contrast, very little degradation of 1,2‐dichloropropane (1,2‐DCP) and 1,1‐dichlorethane (1,1‐DCA) was observed in the anaerobic microcosms, but nutrient addition enhanced their degradation in the aerobic biotic microcosms. The aerobic degradation half‐lives for 1,2‐DCP and 1,1‐DCA were 63 and 56 days, respectively. Evaluation of in situ chemical oxidation (ISCO) demonstrated that chelate‐modified Fenton's reagent was effective in degrading aqueous‐phase PCE, TCE, 1,1,1‐TCA, 1,2‐DCP, etc.; however, this approach had minimal effects on solid‐phase contaminants. The observed oxidant demand was 16 g‐H₂O₂/L‐groundwater. The oxidation reaction rates were not highly sensitive to the molar ratio of H₂O₂:Fe²⁺:citrate. A ratio of 60:1:1 resulted in slightly faster removal of chemicals of concern (COCs) than those of 12:1:1 and 300:1:1. This treatment resulted in increases in dissolved metals (Ca, Cr, Mg, K, and Mn) and a minor increase of vinyl chloride. Treatment with zero‐valent iron (ZVI) resulted in complete dechlorination of PCE, and TCE to ethene and ethane. ZVI treatment reduced 1,1,1‐TCA only to 1,1‐DCA and chloroethane (CA) but had little effect on reducing the levels of 1,2‐DCP, 1,1‐DCA, and CA. The longevity test showed that one gram of 325‐mesh iron powder was exhausted in reaction with > 22 mL of groundwater. The short life of ZVI may be a barrier to implementation. The ZVI surface reaction rates (k_sa) were 1.2 × 10^?2 Lm^?2h^?1, 2 × 10^?3 Lm^?2h^?1, and 1.2 × 10^?3 Lm^?2h^?1 for 1,1,1‐TCA, TCE, and PCE, respectively. Based upon the results of this study, in situ bioremediation appeared to be more suitable than ISCO and ZVI for effectively treating the groundwater contamination at the site. © 2004 Wiley Periodicals, Inc.     

Chloroethene dechlorination in acidic groundwater: Implications for combining fenton's treatment with natural attenuation

A sulfuric acid leak in 1988 at a chloroethene‐contaminated groundwater site at the Naval Air Station Pensacola has resulted in a long‐term record of the behavior of chloroethene contaminants at low pH and a unique opportunity to assess the potential impact of source area treatment technologies, which involve acidification of the groundwater environment (e.g., Fenton's‐based in situ chemical oxidation), on downgradient natural attenuation processes. The greater than 75 percent decrease in trichloroethene (TCE) concentrations and the shift in contaminant composition toward predominantly reduced daughter products (dichloroethene [DCE] and vinyl chloride [VC]) that were observed along a 30‐m groundwater flow path characterized by highly acidic conditions (pH = 3.5 ± 0.4) demonstrated that chloroethene reductive dechlorination can continue to be efficient under persistent acidic conditions. The detection of Dehalococcoides‐type bacteria within the sulfuric acid/chloroethene co‐contaminant plume was consistent with biotic chloroethene reductive dechlorination. Microcosm studies conducted with ¹⁴C‐TCE and ¹⁴C‐VC confirmed biotic reductive dechlorination in sediment collected from within the sulfuric acid/chloroethene co‐contaminant plume. Microcosms prepared with sediment from two other locations within the acid plume, however, demonstrated only a limited mineralization to ¹⁴CO₂ and ¹⁴CO, which was attributed to abiotic degradation because no significant differences were observed between experimental and autoclaved control treatments. These results indicated that biotic and abiotic mechanisms contributed to chloroethene attenuation in the acid plume at NAS Pensacola and that remediation techniques involving acidification of the groundwater environment (e.g., Fenton's‐based source area treatment) do not necessarily preclude efficient chloroethene degradation. © 2007 Wiley Periodicals, Inc.     

Evaluation of the adsorption behavior of mixed perfluoroalkyl and polyfluoroalkyl substances onto granular activated carbon and styrene-divinylbenzene resins

Because of the remarkable chemical structure of perfluoroalkyl and polyfluoroalkyl substances (PFAS), as well as the complex conditions of water, selecting an appropriate adsorbent for treating PFAS is critical. Adsorption needs to be environmentally friendly, low cost, and consider the types of adsorbents that work well in mixed PFAS solutions. In the present study, we used mixed PFAS to estimate the PFAS activity. This research aimed to evaluate and compare the efficacy of the adsorption of PFAS from water using different adsorbents: granular activated carbon (GAC), IRA 910 (strong anion resin), and DOWEX MB-50 (mixed exchange resin). Batch adsorption isotherms and kinetic studies were performed for perfluorooctanoic acid (PFOA), perfluorooctane sulfonic acid (PFOS), and perfluorohexane sulfonic acid (PFHxS). Freundlich models consistently described the kinetic behavior with a high correlation coefficient (R² > 0.98). PFAS adsorption capacities on GAC and IRA910 were dependent on the chain length (PFOS > PFOA > PFHxS). The adsorption capacity of DOWEX MB-50 decreased because of the sulfonate effects (PFOS > PFHxS > PFOA). The rate constants (k₂) that represented the adsorption of PFAS on different adsorbents observed within 96 h were accurately determined by the pseudo-second-order (PSO) model. GAC achieved followed the relationship k₂(PFOS) > k₂(PFOA) > k₂(PFHxS). Furthermore, k₂ of IRA910 decreased in the order of k₂(PFOA) > k₂(PFOS) > k₂(PFHxS), implying that IRA910 promoted hydrophobicity more significantly on the adsorption of PFCAs than perfluoroalkane (-alkyl) sulfonic acids. The kinetics of DOWEX MB-50 revealed k₂(PFHxS) > k₂(PFOS) > k₂(PFOA) because gel-type resins like DOWEX MB-50 are more suitable for shorter-chain PFAS. Further investigation is needed to determine the effect of organic matter under natural conditions and evaluate adsorptive selection caused by operational complexities.     

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

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

The in situ treatment of BTEX,MTBE, and TBA in saline groundwater

A pilot‐scale test was conducted in a saline aquifer to determine if a petroleum hydrocarbon (PHC) plume containing benzene (B), toluene (T), ethylbenzene (E), xylenes (X), methyl tert‐butyl ether (MTBE), and tert‐butyl alcohol (TBA) could be treated effectively using a sequential treatment approach that employed in situ chemical oxidation (ISCO) and enhanced bioremediation (EBR). Chemical oxidants, such as persulfate, have been shown to be effective in reducing dissolved concentrations of BTEX (B + T + E + X) and additives such as MTBE and TBA in a variety of geochemical environments including saline aquifers. However, the lifespan of the oxidants in saline environments tends to be short‐lived (i.e., hours to days) with their effectiveness being limited by poor delivery, inefficient consumption by nontargeted species, and back‐diffusion processes. Similarly, the addition of electron acceptors has also been shown to be effective at reducing BTEX and associated additives in saline groundwater through EBR, however EBR can be limited by various factors similar to ISCO. To minimize the limitations of both approaches, a pilot test was carried out in a saline unconfined PHC‐impacted aquifer to evaluate the performance of an engineered, combined remedy that employed both approaches in a sequence. The PHC plume had total BTEX, MTBE, and TBA concentrations of up to 4,584; 55,182; and 1,880 μg/L, respectively. The pilot test involved injecting 13,826 L of unactivated persulfate solution (19.4 weight percent (wt.%) sodium persulfate (Na₂S₂O₈) solution into a series of injection wells installed within the PHC plume. Parameters monitored over a 700‐day period included BTEX, MTBE, TBA, sulfate, and sulfate isotope concentrations in the groundwater, and carbon and hydrogen isotopes in benzene and MTBE in the groundwater. The pilot test data indicated that the BTEX, MTBE, and TBA within the PHC plume were treated over time by both chemical oxidation and sulfate reduction. The injection of the unactivated persulfate resulted in short‐term decreases in the concentrations of the BTEX compounds, MTBE, and TBA. The mean total BTEX concentration from the three monitoring wells within the pilot‐test area decreased by up to 91%, whereas MTBE and TBA mean concentrations decreased by up to 39 and 58%, respectively, over the first 50 days postinjection in which detectable concentrations of persulfate remained in groundwater. Concentrations of the BTEX compounds, MTBE, and TBA rebounded at the Day 61 marker, which corresponded to no persulfate being detected in the groundwater. Subsequent monitoring of the groundwater revealed that the concentrations of BTEX continued to decrease with time suggesting that EBR was occurring within the plume. Between Days 51 and 487, BTEX concentrations decreased an additional 84% from the concentration measured on Day 61. Mean concentrations of MTBE showed a reduction during the EBR phase of remediation of 33% while the TBA concentration appeared to decrease initially but then increased as the sulfate concentration decreased as a result of MTBE degradation. Isotope analyses of dissolved sulfate (³⁴S and ¹⁸O), and compound‐specific isotope analysis (CSIA) of benzene and MTBE (¹³C and ²H) supported the conclusions that ISCO and EBR processes were occurring at different stages and locations within the plume over time.     

Evaluation of the effects of PFAS soil adsorption and transformation in the presence of divalent cations under ambient conditions

A bench‐scale study was conducted to evaluate the effect of divalent cations on the adsorption of perfluoroalkyl and polyfluoroalkyl substances (PFAS) onto soil particles. The study entailed batch testing of a synthetic soil mixture under a range of Epsom salt (soluble magnesium sulfate heptahydrate) concentrations. The synthetic soil was produced using a mix of sand, silt, clay, and organic matter that then was mixed and saturated with water collected from a PFAS‐impacted water source. The results indicate that variable concentrations of magnesium (divalent cation) had a minor effect on the sorption of perfluorooctane sulfonate with the highest sorption occurring in the strongest solution of Epsom salt. An unanticipated result of the test involved apparent biomediated transformation of polyfluorinated alkylated sulfonates (fluorotelomers or FTS) to perfluorooctanoic acid, perfluoroheptanoic acid (PFHpA), and perfluorononanoic acid. We believe this is the first time the complete transformation of 6:2 FTS to PFHpA has been observed and reported under ambient surface water‐like conditions within 6 months, a relatively short timeframe.     

Evaluating the longevity of a PFAS in situ colloidal activated carbon remedy

The remediation of per‐ and polyfluoroalkyl substances by injection of colloidal activated carbon (CAC) at a contaminated site in Central Canada was evaluated using various visualization and modeling methods. Radial diagrams were used to illustrate spatial and temporal trends in perfluoroalkyl acid (PFAA) concentrations, as well as various redox indicators. To assess the CAC adsorption capacity for perfluorooctane sulfonate (PFOS), laboratory Freundlich isotherms were derived for PFOS mixed with CAC in two solutions: (1) PFOS in a pH 7.5 synthetic water that was buffered by 1 millimolar NaHCO₃ (K_f = 142,800 mg^1‐a L^a/kg and a = 0.59); and (2) a groundwater sample (pH = 7.4) containing PFOS among other PFAS from a former fire‐training area in the United States (K_f = 4,900 mg^1‐a L^a/kg and a = 0.24). A mass balance approach was derived to facilitate the numerical modeling of mass redistribution after CAC injection, when mass transitions from a two‐phase system (aqueous and sorbed to organic matter) to a three‐phase system that also includes mass sorbed to CAC. An equilibrium mixing model of mass accumulation over time was developed using a finite‐difference solution and was verified by intermodel comparison for prediction of CAC longevity in the center of a source area. A three‐dimensional reactive transport model (ISR‐MT3DMS) was used to indicate that the CAC remedy implemented at the site is likely to be effective for PFOS remediation for decades. Model results are used to recommend remedial design and monitoring alternatives that account for the uncertainty in long‐term performance predictions.     

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.     

Influence of groundwater conditions and co‐contaminants on sorption of perfluoroalkyl compounds on granular activated carbon

Per and polyfluoroalkyl substances (PFAS) are emerging and persistent organic pollutants that have been detected in many environmental media, humans, and wildlife. A common method to effectively remove PFAS from water is adsorption by activated carbon. Preliminary sorption experiments were conducted using five characterized Calgon Corporation coal‐based granular activated carbon (GAC; F100, F200, F816, F300, and F400), one coconut‐based GAC (CBC‐OLC 12 × 30), and one Jacobi Corporation coal‐based GAC (Omni‐G 12 × 40). Sorption of four representative PFAS onto each GAC was measured to select the most favorable carbon sources. F400 and CBC were chosen based on their performance in preliminary PFAS sorption experiments and contrasting properties. Freundlich and Langmuir isotherm models were developed for perfluorooctanoic acid (PFOA) and perfluorooctanoic sulfonate (PFOS) at an initial concentration of 1 mg/L. Sorption capacities were determined for PFOA and PFOS individually and in the mixture. Individual compounds showed higher sorption than when present in the mixture for both PFOA and PFOS. PFOS showed higher sorption than PFOA both individually and in the mixture and F400 showed higher sorption capacity than CBC. The presence of co‐contaminants (kerosene, trichloroethylene, and ethanol), and variations in groundwater conditions (pH, presence of anions, naturally occurring organic matter, and iron oxides) demonstrated limited impact on the sorption of PFAS onto GAC under the experimental conditions tested.     

The in situ treatment of PFAS within porewater at the air–water interface of a PFAS source zone

The treatment of per- and polyfluoroalkyl substances (PFAS) within groundwater is an emerging topic, with various technologies being researched and tested. Currently, PFAS-impacted groundwater is typically treated ex situ using sorptive media such as activated carbon and ion exchange resin. Proven in situ remedial approaches for groundwater have been limited to colloidal activated carbon (CAC) injected into aquifers downgradient of the source zones. However, treatment of groundwater within the source zones has not been shown to be feasible to date. This study evaluated the use of CAC to treat dissolved PFAS at the air–water interface within the PFAS source zone. Studies have shown that PFAS tends to preferentially accumulate at the air–water interface due to the chemical properties of the various PFAS. This accumulation can act as a long-term source for PFAS, thus making downgradient treatment of groundwater a long-term requirement. A solution of CAC was injected at the air–water interface within the source zone at a site with PFAS contamination using direct push technology. A dense injection grid that targeted the interface between the air and groundwater was used to deliver the CAC. Concentrations of PFAS within the porewater and groundwater were collected using a series of nine lysimeters installed within the vadose and saturated water columns. A total of six PFAS were detected in the porewater and groundwater including perfluorobutanoic acid (PFBA), perfluoropentanoic acid (PFPeA), perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), and perfluorononanoic acid (PFNA). Detectable concentrations of PFAS within the pore and groundwater before treatment ranged from values greater than 300 µg/L for PFPeA to less than 3 µg/L for PFNA. Following the injection of the CAC, monitoring of the porewater and groundwater for PFAS was conducted approximately 3, 6, 9, 12, and 18 months postinjection. The results indicated that the PFAS within the porewater and groundwater at and near the air–water interface was effectively attenuated over the 1.5-year monitoring program, with PFAS concentrations being below the method detection limits of approximately 10 ng/L, with the exception of PFPeA, which was detected within the porewater during the 18-month sampling event at concentrations of up to 55 ng/L. PFPeA is a five carbon-chained PFAS that has been shown to have a lower affinity for sorption onto activated carbon compared to the longer carbon-chained PFAS such as PFOA. Examination of aquifer cores in the zone of injection indicated that the total organic carbon concentration of the aquifer increased by five orders of magnitude postinjection, with 97% of the samples collected within the target injection area containing activated carbon, indicating that the CAC was successfully delivered into the source zone.     

Bioremediation of a former dry cleaner using potassium lactate

Chlorinated solvents were released to the surficial groundwater underneath a former dry cleaning building, resulting in a groundwater plume consisting of high concentrations of trichloroethene (TCE) and cis‐1,2‐dichloroethene (cis‐1,2‐DCE) and low concentrations of tetrachloroethene (PCE) and vinyl chloride. The initial remedial action included chemical oxidation via injection of 14,400 gallons of Fenton's Reagent in March 2002, and an additional 14,760 gallons in April 2002. A sharp reduction of contaminant concentrations in groundwater was observed the following month; however, rebound of contaminant concentrations was evident as early as October 2002. A source area of PCE‐impacted soils was excavated in June 2004. Following the excavation, Golder Associates Inc. (2007) implemented a biostimulation plan by injecting 55 gallons of potassium lactate (PURASAL® HiPure P) in September 2005, and again in February 2006. Comparing the preinjection and postinjection site conditions, the potassium lactate treatments were successful in accomplishing a 40 to 70 percent reduction in mass within four months following the second injection. Elevated vinyl chloride concentrations have persisted through both injection events; however, significant vinyl chloride reduction has been observed in one well with the highest total organic carbon (TOC) concentrations following each injection. © 2008 Wiley Periodicals, Inc.