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All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

PFAS remediation: Evaluating the infrared spectra of complex gaseous mixtures to determine the efficacy of thermal decomposition of PFAS

Due to their widespread production and known environmental contamination, the need for the detection and remediation of per- and polyfluoroalkyl substances (PFAS) has grown quickly. While destructive thermal treatment of PFAS at low temperatures (e.g., 200 to 500oC) is of interest due to lower energy and infrastructure requirements, the range of possible degradation products remains underexplored. To better understand the low temperature decomposition of PFAS species, we have coupled gas-phase infrared spectroscopy with a multivariate curve resolution (MCR) analysis and a database of high-resolution PFAS infrared reference spectra to detect and quantify a complex mixture resulting from potassium perfluorooctanesulfonate (PFOS-K) decomposition. Nine prevalent decomposition products (namely smaller perfluorocarbon species) are identified and quantified.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Degradation of Poly- and Perfluoroalkyl Substances (PFAS) in Water via High Power, Energy-Efficient Electron Beam Accelerator

The goal of the 2-year workplan was to see if electron beam (EB) could be used to break down a sub-set of the larger chemical family of per and polyfluoroalkylated substances (PFAS) in an energy efficient and economical manner when compared to conventional water treatment technologies. Year one (Y1) work focused on sample EB treatment work in the Fermi National Accelerator Laboratory’s (FNALs) Accelerator Applications Demonstration and Development (A2D2) EB accelerator. While there are reportedly thousands of types of PFAS, for the point of most of the work herein, a small subset was examined, typically perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA). PFOA and PFOS are two of the most well studied PFAS and are studied for baseline evaluations and are considered most useful. The work from Y1 provided information about the optimal operating parameters and additives to use when treating PFOS and PFOA via EB. The data were then used to see where in a water treatment system an EB accelerator would be best suited to treat PFAS. A conventional water treatment technology, GAC, was then compared to e-beam treatment technology with respect to energy and costs for treatment. In year two (Y2), several conventional e-beam accelerator designs, and FNAL’s developmental compact SRF accelerator design, were evaluated for their suitability in PFAS treatment, from an energy efficiency and cost standpoint. Several EB parameters were evaluated and optimized for the removal of PFOA and PFOS from water at normal pressure and temperature, measured as total PFAS removal. Under the optimized test conditions both PFOA showed complete destruction to inorganic fluoride, and PFOS to inorganic fluoride and sulfate, with mass balance. The effect on PFAS removal relative to solution pH, total EB dose, EB dose rate, dissolved oxygen concentration (DO), temperature, and initial PFAS concentration were evaluated. In general, PFOA was easier to destroy than PFOS. Degradation products, typically observed under less-than-optimal EB conditions, provided insight to degradation mechanisms. Products were identified to rule out possible deleterious biproduct formation. The water radiolysis radical reaction kinetics with PFOS and PFOA were not dependent on the initial concentration over 5-orders of magnitude from 2 μg/L to 20 mg/L. This is thought to be because there was an overabundance of the reactive water radiolysis radicals relative to PFAS molecules and largely attributed to aqueous electrons. The reaction rates appeared to be diffusion limited. Testing at higher concentrations (100-200 mg/L) showed a decrease in removal efficiency, suggesting alternative kinetics, possibly second order rates, at higher concentrations. In all, we successfully defined a set of optimal EB parameters to treat PFOA and PFOS at concentrations of 20 mg/L in water with destruction efficiencies near 100%. We further tested the optimized EB parameters with other types of PFAS, including shorter and longer fluorocarbon chain homologs of PFOA and PFOS, and PFAS with alternative functional groups such as sulfonamides. Based on our results EB can be optimized as an effective destructive technology for removing PFAS from water. The conditions optimized for PFOA and PFOS were less effective with ultra-short fluorocarbon compounds like TFMS, PFES, PFPS and PFBS, and likely require re-optimization of parameters to them. In all, it was determined that from a cost and energy efficiency standpoint, EB would be best applied to waste streams with relatively high concentrations of PFOS and PFOA and is not as cost effective as GAC treatment for removing low concentrations of PFAS from water. Higher concentrations of PFAS can be found in the wastewater of conventional treatment processes such as RO and IE and therefore EB may be used to supplement such treatment technologies. Some real-world IE regeneration wash water and RO reject water containing higher concentrations of PFAS and obtained from pilot scale industrial wastewater treatment system at a fluorochemical manufacturing facility, showed that EB could remove PFAS from such types of wastewaters. The IE regenerant wash water appeared to be the most efficient of the two types of wastewaters tested. However, some further optimization of the EB parameters for the specific PFAS types present in those wastewaters may be required. Also, the effects of co-present TOC and mineral salts should be considered during such optimization efforts. From the experimental Y1 results it was seen that the aqueous electron drives degradation of the PFAS. In a hypothetical water treatment skid using EB for PFAS destruction the parameters of the system should be optimized to promote aqueous electron production. Before EB treatment, the PFAS should be preconcentrated when possible, the pH should be raised to pH 10 or higher to enhance aqueous electron production, and the water should be nitrogen purged to remove dissolved oxygen to minimize aqueous electron scavenging. An excel spreadsheet was created that calculates optimal conditions based on inlet PFAS concentration and desired outlet concentration, by optimizing the accelerator power, dose rate, water treatment rate, pH and dissolved oxygen levels to reach the desired endpoint. Given this information on accelerator operating conditions five different EB accelerator systems were compared. One EB system was a continuous-wave, linear superconducting accelerator being designed at Fermilab. Three other EB systems (IMPELA at 5% and 25% duty factor and the ILU-14) were normal conducting pulsed linear accelerators. The fifth system was an IBA Rhodotron which is a normal conducting, circular, continuous-wave accelerator. The accelerator efficiency (% of the incoming power that is used in water treatment) was the dominating factor in accelerator choice. The radio frequency (RF) power supply and the accelerator design (superconducting versus warm technology) drive the accelerator efficiency. The IBA Rhodotron was seen to be the most energy efficient commercially available technology with a wall-plug (total) power efficiency of 43% at 400 kW. The Fermilab design, with a prototype for a different application currently being fabricated, was the most energy efficient at 55% when driven by a Klystron RF power supply and as high as 77% when powered by a magnetron. As the Fermilab design was the most energy efficient by approximately 10-30%, further design work was done on the accelerator and beam delivery system specific to the destruction of PFAS in water. The Fermilab design is unique from industrial accelerators in that is superconducting. Superconducting technology allows for the acceleration of electrons without losses. The accelerator must be cooled to below the point where it is superconducting and is operated around 4 degrees Kelvin. The bulk of the design work for the accelerator is on making the accelerator as energy efficient as possible so that it does not require liquid helium and can be cooled with conduction cooling via cryocoolers. Final design work resulted in an EB accelerator that would operate at minimally 200 kW and 10 MeV. Prototype construction would cost $\$ $7.8 million dollars when driven by a Klystron power supply. A second version of the same accelerator would cost $\$ $5.5 million dollars when driven by a magnetron that is still under development. The commercially available 300 kW IBA Rhodotron cost was estimated at approximately $\$ $9 million. While it is hard to directly compare, an operational GAC system used by 3M for groundwater treatment capital cost (2022 dollars) was estimated to cost $\$ $3.3 million. While the capital expense of the EB accelerator systems was higher than GAC, the accelerator EB treatment would result in destruction of the PFAS and not just sequestration of PFAS to form a new waste stream that requires further treatment or disposal. The operating cost to destroy the PFAS via 400 kw EB system was less than $\$ $1000/kg of PFAS destroyed when treating at a 20 mg/L PFAS concentration, compared to GAC with operating costs that calculated at $\$ $27,530 per kg of PFAS sequestered when treating 100 μg/L PFOA and PFOS combined concentration.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

PFAS Removal by Ion Exchange Resins: Background and Knowledge Gaps with Respect to the Hanford Site

Per- and polyfluoroalkyl substances (PFAS) have been a rising concern for the past two decades, with the United States Department of Defense and Environmental Protection Agency investing millions of dollars in research into remediation and clean-up technologies. Due to the environmental persistence, toxicity, biological uptake, and ongoing changes in both federal and state regulatory space, understanding the fate and transport of PFAS compounds has been of growing concern to the US Department of Energy (DOE). The DOE’s Hanford Site is investigating historical use of PFAS and will be doing site characterization for PFAS. Thus, PFAS have not yet been identified as a contaminant concern in regulatory documents. Based on historical records that mention the discharge of aqueous film-forming foam containing PFAS and having on-site fire stations (a risk factor for PFAS contamination), it seems likely that environmental releases of PFAS may have occurred. Pump and treat (P&T) remediation is the selected remedy for multiple groundwater contaminant plumes at Hanford. These P&T systems use ion exchange (IX) as a component of aboveground treatment, with the specific resins depending on the target contaminants. There is potential that these IX resins may be able to remove PFAS from groundwater, but investigation is needed to understand affinity/selectivity and removal capacity given the groundwater composition and the operating conditions. This report provides background on PFAS uses and chemistry, then provides a review of IX resin applications for PFAS, identifying knowledge gaps. Recommendations are provided regarding research needed to address knowledge gaps and acquire information needed to propose IX as a future PFAS remediation technology at the Hanford Site, as well as other U.S. Department of Energy sites. Generally, PFAS compounds are fluorinated substances that contain at least one fully fluorinated methyl or methylene carbon – with a few noted exceptions, any chemical with at least a perfluorinated methyl group (–CF3) or a perfluorinated methylene group (–CF2–) is a PFAS. These chemical compounds are characterized as non-biodegradable, non-reactive, non-photolytic, and hydrolysis resistant. This makes them highly recalcitrant within the environment, however polyfluoroalkyl materials are less recalcitrant as the carbon chains contain C–H bonds which are more easily broken than carbon – fluorine (C–F) bonds. The backbone carbon structures are commonly punctuated with a head group, the most well-known of them are perfluorooctanesulfonic acid and perfluorooctanoic acid, which possess a sulfonate and a carboxylate group, respectively. IX resins are marketed for the removal of PFAS from water systems and industrial water, however, the mechanism of removal is not as well understood as for anion or cation removal. A better understanding of the mechanism of removal would enable the development of IX resins that have improved specificity for PFAS removal. Four knowledge gaps were identified: 1) the effect of dissolved ions on the IX resin PFAS removal effectiveness, 2) the effect of additional primary contaminants of concern (PCOCs) or secondary contaminants of concern (SCOCs) on the effectiveness of PFAS via IX resin, 3) the mechanisms of PFAS removal from water, and 4) practical solutions to IX resin regeneration and waste disposal.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
NASA NTRS2023

Fire Station #2, Former Sewage Treatment Plant #17, and Towway Area-SWMU 114 PFAS Site Assessment Progress Report Kennedy Space Center, Florida

This PFAS Site Assessment Progress Report (SAPR) presents the findings of the 2022 PFAS investigation conducted from November 2021 through August 2022 at Solid Waste Management Unit (SWMU) 114 located within Kennedy Space Center (KSC), Florida. SWMU 114 includes area around Fire Station #2, Former Sewage Treatment Plant #17, the southern portion of the Shuttle Landing Facility Runway, Remote Launch Vehicle Hangar, and the Towway area. Fire Station #2 was constructed in 2008 and is currently active, housing fire station personnel and equipment, including aqueous film forming foam (AFFF). Releases of AFFF has occurred at SWMU 114. Previous environmental assessments have been performed at SWMU 114, including soil, groundwater, and surface water sampling for volatile organic compounds, polycyclic aromatic hydrocarbons, total petroleum hydrocarbons, and metals. No active remediation has been performed at the SWMU 114. PFAS site assessment field activities were conducted at SWMU 114 from November 2021 through August 2022. During the 2021-2022 Site Assessment, 124 direct-push samples were collected from 27 locations, 17 surface water samples were collected from 15 locations, 41 groundwater samples were collected from 37 newly installed monitoring wells, five concrete samples were collected from four locations, and one asphalt sample was collected. Additionally, two soil borings were advanced to 60 feet for lithologic descriptions, ten staff gauges were installed, and one round of water level measurements were collected from monitoring wells and staff gauges for groundwater flow determination. All groundwater and surface water samples were analyzed for 25 PFAS analytes by USEPA Method 537M. Concrete, and asphalt samples were analyzed by synthetic precipitation leaching procedure (SPLP) PFAS analysis by USEPA Modified Method 537M. Groundwater results were compared to the most recent Regional Screening Levels (RSLs) published by USEPA for residential tap water (USEPA, 2022a) to determine the extent of PFAS contamination at SWMU 114 for six PFAS analytes (PFOA, PFNA, PFBS, PFHxS, PFOS, and GenX). Surface water results were compared to the FDEP surface water screening levels (SW SLs) (FDEP, 2020) for PFOA and PFOS. The PFAS investigation concluded that groundwater exceeding RSLs extends east and south to Banana Creek and west to approximately the center of the SLF runway. The extent of PFAS is approximated to the north, to an area between Sharkey Road and Astronaut Road, where samples below the RSLs do not fully bound SWMU 114. At least two distinct PFAS source areas are located near Fire Station #2 and along Towway, at S114-MW0007S, within SWMU 114. Groundwater head measurements indicate that flow at SWMU 114 is generally similar across the shallow and intermediate water tables. A northeast to southwest trending groundwater divide is located near the middle of Towway where groundwater southeast of the divide flows to the south and groundwater northwest of the divide flows to the west. The groundwater divide generally separates the two areas of higher PFAS concentrations. Surface water samples indicated concentrations of PFOS above the SW SLs in surface water bodies across the site. Further assessment and sampling are required to better understand the interaction between groundwater and surface water at SWMU 114. Concrete and asphalt samples collected confirm that a significant release of AFFF occurred near the stormwater pond northwest of Fire Station #2. Additional concrete samples surrounding Fire Station #2 and at the northwest and southeast edges of the SLF tarmac indicate elevated PFOS concentrations. These results indicate that discharges of AFFF in these locations have infiltrated into asphalt and concrete and may act as a continuing source of PFAS to groundwater and surface water after rain events. Additional direct-push samples are required to delineate PFAS at SWMU 114. Samples may need to extend beyond the Former SLF Rescue Building and Morpheous Test Site to delineate PFAS in groundwater. Monitoring wells should be sampled and gauged quarterly to determine if seasonal impacts are observable, especially in shallow wells near surface water features. Furthermore, surface water samples should be collected from additional ditches to further define the extent of surface water impacts at SWMU 114 and extending along the SLF runway. Staff gauges should be gauged quarterly with groundwater gauging to determine surface water flow and interaction with groundwater. The PFAS sampling results and path forward for SWMU 114 were presented to the KSC Remediation Team in October 2022. Once the PFAS SAPR is approved, it will be submitted to the Florida Department of Environmental Protection.

Howard Franklin Fowler↗
DOE OSTI2025

Groundwater flowpath characteristics drive variability in per- and polyfluoroalkyl substances (PFAS) loading across a stream-wetland system

Groundwater dependent ecosystems in areas with industrial and military land use are at risk of direct exposure to a wide range of contaminants, including PFAS chemicals. Glaciated terrain often has mixed high and low permeability sediments coupled with groundwater flow-through lake features. These hydrogeologic attributes create highly complex ‘source to seep’ dynamics that make spatiotemporal contaminant transport patterns difficult to predict. We investigated one such system in detail using a suite of heat-tracing and chemical methods. Numerous (n=57) preferential groundwater discharge zones (vertical flux rates ranging 0.2 to 3.2 m/d) were identified across the upper Quashnet River stream-wetland system in Mashpee, MA, USA, adjacent to an Air Force Base with several known PFAS source areas. Surface-water and groundwater samples were collected and analyzed (n=145) for precursors and terminal PFAS compounds between March and September 2022. Samples were collected at identified seeps along the Quashnet River (n=59), from wells upgradient from the stream-wetland system (n= 44), from contributing flow-through kettle lakes (n=8), and at multiple locations along the Quashnet River (n=34). Samples from seeps and wells had measured PFAS concentrations ranging from non-detect to approximate 3,500 ng/L (mean= 1,650 ng/L), and a range of deuterium excess values (3.2 to 15.9 per mil) indicative of varying degrees of groundwater-lake interaction prior to emergence at the discharge zones. Groundwater-lake interaction along flowpaths that sourced the sampled seeps was farther supported by significant correlations (p < 0.01) between deuterium excess and %PFAS precursors, and between %PFAS precursors and multiple terminal PFAS compounds (e.g., PFPeS, PFBS, PFHxS). However, some sampled seeps contributing groundwater to the stream-wetland system had much higher total PFAS concentrations (>1000 ng/L) than the upgradient kettle lakes, despite showing lake (evaporative) isotopic signatures, indicating the potential for groundwater flowpath convergence at wetland discharge zones and the influence of lakebed PFAS precursor reactions. PFAS compounds and water isotopic composition at sampled multilevel groundwater wells, rivers, lakes, and seeps suggest that a complex mixture of source groundwater and flowpath characteristics are responsible for diverse observed PFAS mixtures at preferential discharge zones across the stream-wetland system. Further, total PFAS loading patterns to the Quashnet River via groundwater discharge remained remarkably similar from winter to summer to fall conditions, despite a regional dry period in late summer 2022 with the upper river channel completely drying. This work addresses gaps in the existing PFAS literature by demonstrating the importance of subsurface fate and transport on PFAS compound concentrations in controlling contaminant mass loading in preferential groundwater discharge zones and presents a transferrable field toolkit for efficient characterization of spatially preferential PFAS transport dynamics.

Contaminant transport↗
DOE OSTI2024

Diverse PFAS produce unique transcriptomic changes linked to developmental toxicity in zebrafish

Per- and polyfluoroalkyl substances (PFAS) are a widespread and persistent class of contaminants posing significant environmental and human health concerns. Comprehensive understanding of the modes of action underlying toxicity among structurally diverse PFAS is mostly lacking. To address this need, we recently reported on our application of developing zebrafish to evaluate a large library of PFAS for developmental toxicity. In the present study, we prioritized 15 bioactive PFAS that induced significant morphological effects and performed RNA-sequencing to characterize early transcriptional responses at a single timepoint (48 h post fertilization) after early developmental exposures (8 h post fertilization). Internal concentrations of 5 of the 15 PFAS were measured from pooled whole fish samples across multiple timepoints between 24–120 h post fertilization, and additional temporal transcriptomics at several timepoints (48–96 h post fertilization) were conducted for Nafion byproduct 2. A broad range of differentially expressed gene counts were identified across the PFAS exposures. Most PFAS that elicited robust transcriptomic changes affected biological processes of the brain and nervous system development. While PFAS disrupted unique processes, we also found that similarities in some functional head groups of PFAS were associated with the disruption in expression of similar gene sets. Body burdens after early developmental exposures to select sulfonic acid PFAS, including Nafion byproduct 2, increased from the 24–96 h post fertilization sampling timepoints and were greater than those of sulfonamide PFAS of similar chain lengths. In parallel, the Nafion byproduct 2-induced transcriptional responses increased between 48 and 96 h post fertilization. PFAS characteristics based on toxicity, transcriptomic effects, and modes of action will contribute to further prioritization of PFAS structures for testing and informed hazard assessment.

59 BASIC BIOLOGICAL SCIENCES↗
NASA NTRS2023

Sewage Treatment Plant #1 Area, SWMU 117 Per- and Polyfluoroalkyl Substances (PFAS) Site Assessment Progress Report

This Per- and Polyfluoroalkyl Substances (PFAS) Site Assessment (SA) Progress Report (SAPR) discusses the investigation activities and findings for the Sewage Treatment Plant #1 (STP1) Area located at Kennedy Space Center (KSC), Florida (Figure 1-1). This site has been designated Solid Waste Management Unit (SWMU) 117 under KSC’s Resource Conservation and Recovery Act (RCRA) Corrective Action Program, as the sewage treatment plant and associated areas were identified as a potential source of PFAS to the environment. This PFAS SAPR was prepared by Tetra Tech, Inc., for the National Aeronautics and Space Administration (NASA) under Indefinite Delivery Indefinite Quantity Contract 80KSC019D0011-80KSC019F0070. This is the first progress report to document on-going SA activities; supplemental progress reports will be provided as additional data is collected. PFAS SA activities were conducted between April 2020 and March 2022 to collect additional data to supplement the existing datasets to better understand the extent of PFAS impacts to the environment in the STP1 Area. The SA for the STP1 Area covers an approximately 130-acre investigation area with multiple structures and buildings. The focus of the SA is the STP1 Complex and associated structures, including the former Polishing Pond, former Sludge Disposal8 Area, and former Spray Field. The STP1 Complex is located in the KSC Industrial Area, at the southwest corner of 4th Street SE and C Avenue SE. The STP1 Complex is located approximately ¼-mile south and downgradient of the Fire Station #1 site (SWMU 116), which is also currently undergoing a PFAS SA because of potential releases of PFAS-containing aqueous film-forming foam (AFFF). During the SA, a total of seven soil, 131 groundwater direct push technology (DPT), 24 groundwater monitoring well, and 11 surface water samples were collected between April 2020 and March 2022. Monitoring well samples were analyzed for 18 PFAS compounds, with all other samples analyzed for 28 PFAS compounds. The SA sample results were used along with historical results to evaluate the extent of PFAS impacts to the environment in the STP1 Area. Data generated to date and prior results were screened against the United States Environmental Protection Agency (USEPA) May 2022 Tap Water Regional Screening Levels (RSL) for groundwater and residential RSLs for soil (hazard quotient of 0.1). Surface water results were screened against the State of Florida Human Health Surface Water Screening Levels (SWSLs). Results from the SA showed exceedances of the applicable screening criteria for groundwater and surface water. Considering the current and historical dataset, PFOS is the prevalent PFAS compound. Based on these results, additional groundwater DPT and surface water sampling should be considered for PFAS analysis, focused on evaluating surface water bodies in the southeast portion of the Industrial Area, which discharge into the Banana River. Additionally, installation of monitoring wells should be considered to evaluate the interaction between the groundwater and surface water at the site. Collection of additional samples for TOC analysis should also be considered from representative groundwater (saturated soils) and surface water locations to further evaluate potential correlations between PFAS and TOC to provide a more comprehensive dataset to assist in fate and transport analyses.

Sewage Treatment Plant↗
DOE OSTI2025

Functionalized Porous Polymer Networks as High-Performance PFAS Adsorbents

Toxic per- and polyfluoroalkyl substances (PFAS) are now found in nearly every water source on the planet. Exposure to these molecules can have negative health consequences, but the low concentration of PFAS relative to other solutes in water makes their removal challenging. Adsorbents offer a promising treatment route, but often exhibit low selectivities and removal capacities, as well as slow kinetics. The performance in these metrics can be improved by chemically optimizing PFAS binding sites and maximizing PFAS-adsorbent interactions. To explore how to achieve this, a porous polymer network solid (PPN-6, also known as PAF-1) was postsynthetically modified with various chemical moieties capable of leveraging unique combinations of electrostatic, hydrogen-bonding, hydrophobic, and fluorophilic interactions with PFAS molecules. Batch adsorption experiments and computational studies revealed that electrostatic and hydrogen-bonding interactions drive short-chain PFAS adsorption, while hydrophobic and fluorophilic interactions improve long-chain PFAS adsorption. In complex water matrices, a combination of electrostatic and fluorophilic interactions led to the greatest total PFAS removal. The best-performing material, functionalized with a fluorinated alkylammonium (PPN-6-FNDMB), selectively adsorbs PFAS with high capacity (up to 4.0 mmol/g) and rapid kinetics (equilibrium reached in <30 s). Furthermore, PPN-6-FNDMB outperforms several commercial adsorbents, achieving near-complete removal of 21 different PFAS from a groundwater sample collected at a US Air Force base. The PFAS could subsequently be desorbed from PPN-6-FNDMB, concentrating them by a factor of over 50 times. The recycled PPN-6-FNDMB could then be reused with minimal losses in long-chain PFAS adsorption capacity over four cycles.

Pezoulas, Ethan R↗
NASA NTRS2024

Hydrocarbon Burn Facility, SWMU 007 Per- and Polyfluoroalkyl Substances (PFAS) Assessment Report Addendum

This document discusses the Per-and Polyfluoroalkyl Substances (PFAS) assessment activities performed from May through August 2023 at the Hydrocarbon Burn Facility (HBF) located at Kennedy Space Center (KSC), Florida. HBF was used for firefighting training between 1966 and 1994. Aqueous film-forming foams (AFFFs) that contained PFAS were used as suppressants for fighting petroleum fuel fires during training. PFAS sampling was first completed at HBF in 2015. This PFAS Assessment Report Addendum (ARA) is a continuation of sampling efforts, with an overall objective to further delineate PFAS concentrations in groundwater to the pGCTLs and the United States Environmental Protection Agency (EPA) Tapwater Regional Screening Levels (RSLs) dated November 2023 and better understand groundwater to surface water interaction at the Site. The field activities presented in this PFAS ARA were conducted between May and August 2023 and included the collection of 132 direct push groundwater samples and the collection of five colocated surface water, sediment, and pore water samples from locations south/southeast of HBF in August 2023. Exceedances of the pGCTLs and Tapwater RSLs were observed in the direct push groundwater results; however, groundwater has been delineated to the pGCTLs. Exceedances of the Florida provisional Surface Water Screening Levels (pSWSLs) were observed in surface water and porewater, and concentrations of PFAS in these media confirm PFAS migration within surface channels to the south of the HBF site area. Maximum sediment concentrations, which correlate with the maximum surface water and porewater concentrations, demonstrate that PFAS impacted surface water is the source of sediment impacts. Overall, elevated concentrations of PFAS are centered on the HBF site area that trend north and south along the surface water filled swales and along the edge of Banana River. Based on analytical results, not all surface water features in this area exhibit evidence of transport. PFAS migration/transport appears to be more dominant in surface water features during the wet season. Discharges to the Banana River primarily occur where surface water facilitates transport. In contrast, groundwater transport is more effective during the dry season. During precipitation events in either the dry season or the wet season, there appears to be migration from the intermediate groundwater zone to the shallow zone into the surface water features. Additional sampling and data collection is recommended to support further refinement of PFAS groundwater delineation, a remedial alternative evaluation, and the fate and transport model.

Jennifer Buel↗
DOE OSTI2023

Development of Scalable Reactive Transport Framework for PFAS

Research on PFAS chemicals is extensive and covers all aspects, including analytical quantification, determination of properties, toxicology, ex situ treatment, and in situ remediation. PFAS chemicals are very stable and thus persistent/recalcitrant in the environment. Although there are many unknowns about PFAS chemicals, degradation pathways, reaction rates, etc., many different sorption, oxidation, reduction, biological, and innovative treatment approaches are being developed. Sorption with activated carbon is currently the only fully available in situ treatment technology for PFAS-impacted groundwater. Given the wide array of PFAS chemicals and transformation products, remediation may need multi-step treatment trains to fully address the PFAS contamination. The work here provides kinetic reaction modules that represent an initial cut at functionality representing PFAS migration and reaction in groundwater aquifer flow and transport models. One reaction kinetics module provides a method to model kinetically limited adsorption using a mass transfer model. The second reaction module represents biological transformation of 8:2 FTOH and daughter species, illustrating how a complex reaction pathway network can be represented. Both reaction modules allow for spatially variable parameter values so that a variety of remediation approaches (e.g., a PRB or volumetric treatment or variations in geochemical conditions) can be simulated. The intent with these PFAS reaction modules is to provide tools for practitioners to aid in the selection, design, and assessment of potential in situ PFAS remediation strategies. It is anticipated that, as PFAS remediation technologies and scientific understanding advances, these modules would be refined or replaced to match new knowledge.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Per- and polyfluoroalkyl substances (PFAS) in fish collected from the Rio Grande and reservoirs in northern New Mexico

Per- and polyfluoroalkyl substances (PFAS) are a group of industrial and commercial chemicals widely used throughout the world due to their beneficial chemical properties. Because of their widespread use, their chemical stability, and their ability to be transported over long distances through atmospheric deposition and movement through waterways, PFAS are found throughout most aquatic ecosystems; yet large sampling gaps exist among reservoir and river ecosystems in the desert southwest of the United States. In this study, we examine PFAS concentrations in the tissue of fish (catfish [channel and blue], common carp, smallmouth bass, northern pike, walleye, white crappie and white sucker) collected in northern New Mexico, including examining PFAS composition and concentration relative to trophic level distribution. We collected fish from two man-made reservoirs and from the Rio Grande. We then collected muscle and liver tissues from fish specimens, which were screened for 39 PFAS compounds. We detected PFAS compounds in most fish tissue sampled, including the biomagnification of PFAS compounds within liver samples, with PFOS concentrations ranged from 1.13 to 350.1 (64.4 average) times higher in the liver samples compared to muscle samples. Most PFAS concentrations within muscle samples were within the range of atmospheric transportation previously reported and average tissue concentrations of PFAS were calculated to be 2.02 ± 1.81 ng g -1 . Using stable isotopes as a predictor of trophic-foraging exposure and PFAS concentrations, we noted a correlation between enriched δ 15 N values, which had higher perfluorodecanoic acid concentrations.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2025

PFAS Waste Management for Industrial, Water, and Wastewater Treatment Facilities

Per- and polyfluoroalkyl substances (PFAS), including perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), are widely used in industrial and consumer products due to their unique water and oil repelling properties. These slow-degrading and bio-accumulating compounds, often called "forever chemicals," are not typically removed by conventional industrial and municipal water/wastewater (W/WW) treatment. This tip of the month provides comprehensive strategies for managing PFAS-contaminated waste streams. Understanding the various types of PFAS waste streams is the first step in managing them. Primary PFAS waste includes contaminated process W/WW and solid materials directly from the production and processing of PFAS-containing materials. These might come from manufacturing facilities, firefighting training areas, or other industrial operations where PFAS compounds are used or were historically present. Secondary PFAS waste results from treatment and disposal mechanisms of primary PFAS waste streams, including spent activated carbon, used ion exchange resins, membrane reject streams, PFAS-laden backwash water, landfill leachate, incineration residuals, etc. TABLE 1 lists examples of the most common PFAS waste streams in different industrial facilities.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
NASA NTRSDate not supplied

PFAS Treatment Pilot Study using Granular Activated Carbon at Kennedy Space Center, Florida

Per- and polyfluoroalkyl substances (PFAS) have been found in investigative derived waste (IDW) generated from groundwater sampling and remediation activities conducted at Kennedy Space Center (KSC), Florida. PFAS are exceptionally strong compounds because of carbon-fluorine bonds resulting in resistance to degradation, low chemical reactivity, compound stability, and persistence in the environment. The regulatory status of PFAS is very dynamic. PFAS is not considered a hazardous waste and has no federal or state (Florida) cleanup requirements at this time. Due to the current and unknown future of the regulatory and treatment landscape, non-hazardous IDW, based upon site volatile organic compounds (VOCs) regulated under Title 40 of Federal Regulations part 261, containing PFAS is not being processed for off-site waste disposal under KSC’s Resource Conservation and Recovery Act permit as a proactive precaution. Long-term storage of aqueous IDW in the meantime was determined to be inadequate due to the potential for spills and/or leaks. A very limited number treatment methods are available at this time. To date, granular activated carbon (GAC) and ion exchange technologies have been found to be some of the most consistent treatment options for removing PFAS from aqueous media. Therefore, a pilot study using GAC was developed at KSC to determine the feasibility of treating non-hazardous IDW containing PFAS to reduce the total volume of PFAS waste and minimize the risk of leaks or spills while storing the waste until complete PFAS-destructive treatment options are more readily available. NASA wanted the pilot test to be able to demonstrate the ability to completely remove 18 PFAS compounds and the site VOCs to below the state of Florida groundwater cleanup target levels (GCTLs).

Michael J Deliz↗
DOE OSTI2023

Impacts of divalent cations (Mg 2+ and Ca 2+ ) on PFAS bioaccumulation in freshwater macroinvertebrates representing different foraging modes

Per- and polyfluoroalkyl substances (PFAS) have extensively contaminated freshwater aquatic ecosystems where they can be transported in water and partition to sediment and biota. In this paper, three freshwater benthic macroinvertebrates with different foraging modes were exposed to environmentally relevant concentrations of eight perfluoroalkyl carboxylates (PFCA), three perfluoroalkyl sulfonates (PFSA), and three fluorotelomer sulfonates (FTS) at varying divalent cation concentrations of magnesium (Mg 2+ ) and calcium (Ca 2+ ). Divalent cations can impact PFAS partitioning to solids, especially to sediments, at higher concentrations. Sediment dwelling worms (Lumbriculus variegatus), epibenthic grazing snails (Physella acuta), and sediment-dwelling filter-feeding bivalves (Elliptio complanata) were selected due to their unique foraging modes. Microcosms were composed of synthetic sediment, culture water, macroinvertebrates, and PFAS and consisted of a 28-day exposure period. L. variegatus had significantly higher PFAS bioaccumulation than P. acuta and E. complanata, likely due to higher levels of interactions with and ingestion of the contaminated sediment. “High Mg 2+ ” (7.5 mM Mg 2+ ) and “High Ca 2+ ” (7.5 mM Ca 2+ ) conditions generally had statistically higher bioaccumulation factors (BAF) than the “Reference Condition” (0.2 mM Ca 2+ and 0.2 mM Mg 2+ ) for PFAS with perfluorinated chain lengths greater than eight carbons. Long-chain PFAS dominated the PFAS profiles of the macroinvertebrates for all groups of compounds studied (PFCA, PFSA, and FTS). Furthermore, these results indicate that the study organism has the greatest impact on bioaccumulation, although divalent cation concentration had observable impacts between organisms depending on the environmental conditions. Elevated cation concentrations in the microcosms led to significantly greater bioaccumulation in the test organisms compared to the experimental reference conditions for long-chain PFAS.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2026

Toxicity of Common Fluoropolymers and PFAS on C. Elegans and an Innovative Strategy to Promote in Situ Remediation - 26128

Per- and polyfluoroalkyl substances (PFAS) are a broad class of synthetic chemicals used in a variety of modern technologies and consumer products. PFAS have an alkyl backbone with all or most of the hydrogen (H) atoms replaced with fluorine (F) atoms. PFAS generally fall into one of two categories, they can be non-polymeric with relatively low molecular weights, or long-chain polymers. PFAS are a diverse group of organic compounds that can be solids, liquids, dispersions, or gases. Their mobility and toxicity are influenced by their chain lengths and functional groups. Non-polymeric PFAS are common building blocks for the manufacturing of fluoropolymers. Non-polymeric PFAS are known to be mobile in the environment and some are considered contaminants of emerging concern. Polymeric PFAS, or fluoropolymers, are typically thought to be of low concern, however few systematic investigations into their toxicity have been completed. PFAS, including fluoropolymers and microplastics, have been found in pristine environments and animals located far from site of origin including the arctic and deep ocean.

Jacobs, Stephanie [Savannah River National Laborat↗
NASA NTRS2023

Fire Station #1 Area, SWMU 116 Per- and Polyfluoroalkyl Substances (PFAS) Site Assessment Progress Report Kennedy Space Center, Florida

This Per- and Polyfluoroalkyl Substances (PFAS) Site Assessment (SA) Progress Report (SAPR) discusses the investigation activities and findings for the Fire Station #1 (FS1) Area (formerly known as Fire Station #4) located at Kennedy Space Center (KSC), Florida (Figure 1-1). This site has been designated Solid Waste Management Unit (SWMU) 116 under KSC’s Resource Conservation and Recovery Act (RCRA) Corrective Action Program. This PFAS SA is being managed under SWMU 116 as the fire station was identified as a potential source of PFAS to the environment. This PFAS SAPR was prepared by Tetra Tech, Inc., for the National Aeronautics and Space Administration (NASA) under Indefinite Delivery Indefinite Quantity Contract 80KSC019D0011-80KSC019F0070. This is the first progress report to document on-going SA activities; supplemental progress reports will be provided as additional data is collected. During the SA, a total of six soil, 48 groundwater direct push technology (DPT), eight groundwater monitoring well, and one surface water sample were collected between October 2021 and March 2022. The samples were analyzed for 28 PFAS compounds using the Department of Defense Quality Systems Manual-compliant Method. SA sample results were used along with historical results to evaluate the extent of PFAS impacts to the environment in the FS1 Area. Data generated to date and prior results were screened against the United States Environmental Protection Agency (USEPA) May 2022 Tap Water Regional Screening Levels (RSLs) for groundwater and residential RSLs for soil (hazard quotient of 0.1). Surface water results were screened against the State of Florida Human Health Surface Water Screening Levels (SWSLs). Overall, results from the SA showed exceedances of the applicable screening criteria for soil, groundwater and surface water. Considering the current and historical dataset, perfluorooctanesulfonic acid (PFOS) is the prevalent PFAS compound, which is indicative of AFFF releases. Based on results of the SA, additional groundwater DPT and surface water sampling should be considered, focused on evaluating surface water bodies in the southeast portion of the Industrial Area, which discharge into the Banana River. Additionally, installation of monitoring wells should be considered to evaluate the interaction between groundwater and surface water in the FS1 Area.

PFAS↗
DOE OSTI2024

Atomically Precise Hexanuclear Ce(IV) Clusters as Functional Fluorescent Nanosensors for Rapid One-Step Detection of PFAS

Here, the presence of poly- and perfluoroalkyl substances (PFAS) in the environment is associated with adverse health effects but measuring PFAS is challenging due to the associated high cost and technical complexities of the analysis. Here, the reactivity of atomically precise metal-oxo clusters is reported and the foundation for their use is provided as fluorescent nanosensors for PFAS detection. The material comprises crystalline, water soluble, hexanuclear cerium-oxo clusters [Ce 6 (µ 3 -O) 4 (µ 3 -OH) 4 ] 12+ decorated with glycine molecules (Ce-Gly) characterized by fluorescence emission at 353 nm. The Ce-Gly fluorescence is found sensitive to long chain carboxylated PFAS of CF 3 –(CF 2 ) n –, where n ≥ 6, such as perfluorooctanoic, perfluorononanoic and perfluorodecanoic acids. This unique reactivity leads to a change in the emission spectra in a concentration dependent manner, enabling PFAS detection through ligand exchange and aggregation-induced emission (AIE) enhancement. No significant cross-reactivity from potentially co-existing species, including sulfonated PFAS, octanoic and dodecanoic acids, humic acid, and inorganic ions is observed. With an optimal concentration of 3.3 µg mL -1 Ce-Gly, the method demonstrated detection limits of 0.24 ppb for PFOA and 0.4 ppb for PFNA. These findings highlight the potential of fluorescence-based detection strategies utilizing nanoscale probes such as Ce-Gly as fluorescent probes and nanosensors for PFAS.

77 NANOSCIENCE AND NANOTECHNOLOGY↗
DOE OSTI2023

DOE-VFP; Surface Engineered Multifunctional Zeolite Composite for Photodegradation of Per- and Polyfluoroalkyl substances (PFAS) in Aqueous Medium

Per- and Polyfluoroalkyl substances (PFAS) are widely used compounds proven to bioaccumulate and result in detrimental health effects. On October 18, 2021 the United States Environmental Pollution Agency (EPA) released a strategic roadmap to address PFAS that includes the investment in effective research that accelerates cleanup. Existing water treatment technologies for PFAS removal are based on adsorptive removal, are commonly single-use and result in pollutant-laden waste, leading to costly disposal processes. Here we proposed the development of a zeolite-TiO 2 composite for removal and degradation of PFAS. The composite is advantageous as it can be easily integrated into water treatment facilities, is multifunctional, and minimizes waste through regeneration. We studied the adsorptive capacity of zeolites 13X, 3A, 4A and 5A for an anionic PFAS surrogate, methyl orange (MO). Zeolite 3A showed the highest adsorptive capacity, followed by 4A, 5A, and 13X when incubated with 15 ppm MO for 3 hours. Depositing Au-nanospheres on the zeolites surface reduced MO adsorption for all zeolites. We also investigated the photodegradation capacity of TiO 2 , Fe 2 O 3 , Au-TiO 2 , and Au-Fe 2 O 3 , ranking their performance as TiO2 > Fe2O3 > Au-TiO 2 > Au-Fe 2 O 3 under 254 nm light in a 10 ppm MO solution. Our results highlight the favorable adsorption of small pore size zeolites for PFAS surrogates and the potential of TiO2 as a photocatalyst for PFAS degradation. We can further study and integrate the composite's components at our home institution. Other notable achievements of our VFP team includes the submission of two funding proposals, two poster presentations and one invited talk thus showcasing our progress.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗