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Electron Beam Irradiation for Water Treatment of Per- and Polyfluoroalkyl Substances (PFAS)

Per- and polyfluoroalkyl substances (PFAS) are widely used but are now considered a water contamination risk. Fermi National Accelerator Laboratory’s IARC group has demonstrated that passing water through electron beam radiation can destroy PFAS. This project aims to develop a process to scale the system for bulk water treatment. The key is efficient radiation usage, ensuring that all water receives only the minimum dose. Software was developed for this purpose, consisting of a computational fluid dynamics model (CFD) in COMSOL, which calculates particle trajectories through the radiation area. A MATLAB script integrates the radiation dose of these particles, and statistical analysis is performed to evaluate the radiation utilization efficiency. These models are validated with a flow test where colored dye is injected and optically tracked. Radiation dose is measured by testing under an e-beam to measure the degradation of a PFAS analog.

Mueller, Scott [Northern Illinois U.]↗

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↗

Interactions between Per- and Polyfluoroalkyl Substances (PFAS) at the Water–Air Interface

Per- and polyfluoroalkyl substances (PFAS)--so-called “forever chemicals”--contaminate the drinking water of about 100 million people in the U.S. alone and are inefficiently removed by standard treatment techniques. A key property of these compounds that underlies their fate and transport and the efficacy of several promising remediation approaches is that they accumulate at the water−air interface. This phenomenon remains incompletely understood, particularly under conditions relevant to natural and treatment systems where water−air interfaces often carry significant loads of other organic contaminants or natural organic matter. To understand the impact of organic loading on PFAS adsorption, we carried out molecular dynamics simulations of PFAS at varying interfacial densities. We find that adsorbed PFAS form strong mutual interactions (attraction between perfluoroalkyl chains and electrostatic interactions among charged head groups) that give rise to ordered interfacial coatings. Furthermore, these interactions often involve near-cancellation of hydrophobic attraction and Coulomb repulsion. Our findings explain an apparent paradox whereby PFAS adsorption isotherms often suggest minimal mutual interactions while simultaneously displaying a high sensitivity to the composition and density of interfacial coatings. Consideration of the compounds present with PFAS at the interface has the potential to allow for more accurate predictions of fate and transport and the design of more efficient remediation approaches.

54 ENVIRONMENTAL SCIENCES↗

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↗

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↗

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↗

Fire Station #3 Area, Solid Waste Management Unit (SWMU) 106 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) presents the activities and results associated with PFAS investigation in the Fire Station #3 (FS3) Area located at Kennedy Space Center (KSC), Florida. FS3 (formerly known as Fire Station #6) was previously designated as Solid Waste Management Unit (SWMU) 106 for legacy contaminants that were investigated and still being managed under KSC’s Resource Conservation and Recovery Act (RCRA) Corrective Action Program. This PFAS SA is being managed under SWMU 106 as the fire station was also identified as the potential source of PFAS to the environment in this area.

Sarah Damphouse↗

Hydrocarbon Burn Facility, SWMU 007 PER- and Polyfluoroalkyl Substances (PFAS) Assessment report Addendum Kennedy Space Center, Florida

This document discusses the Per-and Polyfluoroalkyl Substances (PFAS) assessment activities performed from December 2020 through November 2021 at the Hydrocarbon Burn Facility (HBF) located at Kennedy Space Center (KSC), Florida. The HBF site has been designated Solid Waste Management Unit (SWMU) 007 under KSC’s Resource Conservation and Recovery Act (RCRA) Corrective Action Program. This PFAS Assessment Report Addendum (ARA) was prepared by Tetra Tech, Inc., for the National Aeronautics and Space Administration (NASA) under Indefinite Delivery Indefinite Quantity (IDIQ) Contract 80KSC019D0011-80KSC019F0077.

Jennifer M. Buel↗

SERDP PFAS 2.0 - An infrared spectral database for gas-phase quantitation of volatile per- and polyfluoroalkyl substances (PFAS)

We report the construction of a database of vetted infrared spectra specifically targeting volatile fluorocarbon gases that may be emitted during thermal treatment of per- and polyfluoroalkyl substances (PFAS) to assist understanding of treatment processes and improve quantification. To populate this database, protocols derived from the Pacific Northwest National Laboratory (PNNL) infrared spectral database are used, curtailing the species selection for this data set. Each spectrum in the database is a weighted average derived from 10 or more individual measurements at different partial pressures (static method) or flow rates (dissemination method) to yield good fidelity of both strong and weak infrared signatures, with each composite spectrum ranging from = 6500 cm-1 to = 600 cm-1 with an apodized resolution of 0.112 cm-1. This resolution was chosen to fully resolve all spectral features, recognizing that atmospheric pressure broadening results in nearly all ro-vibrational lines having linewidths = 0.1 cm-1. As an example case, application of the database is demonstrated via identification and quantification of dominant 1H-perfluoroheptane and perfluorohept-1-ene fluorocarbon products resulting from thermal decomposition of perfluorooctanoate (PFOA) below 450 °C.

Infrared, Gas-phase spectra, FTIR, Spectral databa↗

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↗

Contractor Support Building #7 Per- and Polyfluoroalkyl Substances (PFAS) Site Assessment Work Plan

This Work Plan documents the proposed field sampling activities for a per- and polyfluoroalkyl substances (PFAS) Site Assessment at the Contractor Support Building (CSB) #7 at Kennedy Space Center (KSC). The Work Plan provides a background of the historical activities that occurred at CSB #7, and the limited environmental investigations performed at CSB #7. The proposed Site Assessment activities at CSB #7 include the advancement of a soil lithologic boring to 60 feet below ground surface, the installation of a staff gauge in site surface water, perform direct push groundwater sampling at eight locations, and collect four surface water samples. Sampling details, depths, and locations are presented in the Work Plan. The Work Plan was presented to the KSC Remediation Team in the form of an Advance Data Package in February 2023. Following STRIVES approval, the CSB #7 PFAS Site Assessment Work Plan will be formally submitted to the Florida Department of Environmental Protection.

Howard Franklin Fowler↗

Former SLF Fire and Rescue Building SWMU #120 Per- and Polyfluoroalkyl Substances (PFAS) Site Assessment Work Plan

This Work Plan documents the proposed field sampling activities for a per- and polyfluoroalkyl substances (PFAS) Site Assessment at the Former Space Shuttle Landing Facility (SLF) Fire and Rescue Building (FRB) at Kennedy Space Center (KSC). The Work Plan provides a background of the historical activities that occurred at the SLF FRB, and the limited environmental investigations performed at the SLF FRB. The proposed Site Assessment activities at SLF FRB includes the collection of soil samples from eight locations, the advancement of a soil lithologic boring to 60 feet below ground surface, the installation of a staff gauge in site surface water, the installation of four monitoring wells, perform direct push groundwater sampling at seven locations, and collect one surface water sample. Sampling details, depths, and locations are presented in the Work Plan. The Work Plan was presented to the KSC Remediation Team in the form of an Advance Data Package in February 2023. Following STRIVES approval, the SLF FRB PFAS Site Assessment Work Plan will be formally submitted to the Florida Department of Environmental Protection.

Howard Franklin Fowler↗

Morpheus Test Area SWMU #119 Per- and Polyfluoroalkyl Substances (PFAS) Site Assessment Work Plan

This Work Plan documents the proposed field sampling activities for a per- and polyfluoroalkyl substances (PFAS) Site Assessment at the Morpheus Test Area (MTA) at Kennedy Space Center (KSC). The Work Plan provides a background of the historical activities that occurred at the MTA, and the limited environmental investigations performed at the MTA. The proposed Site Assessment activities at MTA includes the collection of soil samples from seven locations, the installation of a staff gauge in site surface water, the installation of four monitoring wells, perform direct push groundwater sampling at ten locations, and collect one surface water sample. Sampling details, depths, and locations are presented in the Work Plan. The Work Plan was presented to the KSC Remediation Team in the form of an Advance Data Package in February 2023. Following STRIVES approval, the SLF FRB PFAS Site Assessment Work Plan will be formally submitted to the Florida Department of Environmental Protection.

Howard Franklin Fowler↗

An infrared spectral database for gas-phase quantitation of volatile per- and polyfluoroalkyl substances (PFAS)

We report the construction of a database of vetted infrared spectra specifically targeting volatile fluorocarbon gases that may be emitted during thermal treatment of per- and polyfluoroalkyl substances (PFAS) to assist understanding of treatment processes and improve quantification. To populate this database, protocols derived from the Pacific Northwest National Laboratory (PNNL) infrared spectral database are used, curtailing the species selection for this data set. Each spectrum in the database is a weighted average derived from 10 or more individual measurements at different partial pressures (static method) or flow rates (dissemination method) to yield good fidelity of both strong and weak infrared signatures, with each composite spectrum ranging from = 6500 cm-1 to = 600 cm-1 with an apodized resolution of 0.112 cm-1. This resolution was chosen to fully resolve all spectral features, recognizing that atmospheric pressure broadening results in nearly all ro-vibrational lines having linewidths = 0.1 cm-1. As an example case, application of the database is demonstrated via identification and quantification of dominant 1H-perfluoroheptane and perfluorohept-1-ene fluorocarbon products resulting from thermal decomposition of perfluorooctanoate (PFOA) below 450 °C.

Infrared, Gas-phase spectra, FTIR, Spectral databa↗

Phase II Solid Waste Management Unit (SWMU) Assessment Work Plan Center Wide Per- and Polyfluoroalkyl Substances (PFAS) Potential Release Location (PRL) 237 Kennedy Space Center, Florida

This document presents a description of solid waste management unit (SWMU) assessment activities that will be used to identify additional locations where per- and polyfluoroalkyl substances (PFAS) may have been used at the Kennedy Space Center (KSC). The activities described herein will also be used to identify potential off-Center sources of PFAS and potential background locations for PFAS within KSC.

Krista D Sommerfeldt↗

An e-beam irradiation beamline at Jefferson Lab for 1,4-dioxane and per- and polyfluoroalkyl substances (PFAS) remediation in wastewater

The Upgraded Injector Test Facility (UITF) at Jefferson Lab, providing a beam energy up to 10 MeV, is suitable for wastewater remediation research. To investigate the degradation of 1,4-dioxane and per- and polyfluoroalkyl substances (PFAS), widespread in wastewater and potential to be regulated in near future, a beamline for electron-beam irradiation has been designed, installed and successfully commissioned at the UITF. A solenoid with a peak axial magnetic field of up to 0.28 T and a raster were used to obtain a Gaussian beam profile with a transverse standard deviation of 15 mm. It was applied to irradiate 1,4-dioxane sample filled in the target cell that was designed to let the entire sample receive significant irradiation doses. The dose distribution and absorbed dose, few studied in the current publications, are necessary measures for the degradation mechanism investigation and have been innovatively achieved in this work using simulations which were calibrated with opti-chromic dosimeter rods directly exposed to the electron beam. This approach provides an important way for investigating the environmental remediation impact of electron-beam irradiation.

Li, Xi↗

Predictive Integrated Stratigraphic Modeling (PRISM®) Work Plan Center Wide Per- and Polyfluoroalkyl Substances (PFAS) Potential Release Location (PRL) 237 Kennedy Space Center, Florida

This document presents a description of various site investigation activities that will be used to improve the conceptual site model (CSM) at the Kennedy Space Center (KSC) to develop a better understanding of the fate and transport of per- and polyfluoroalkyl substances (PFAS) in groundwater and surface water. The activities proposed herein include three primary tasks: a sequence stratigraphic analysis, groundwater and surface water gauging and sampling, and a stormwater pollutant modeling analysis.

PFAS↗

Uptake of individual and mixed per- and polyfluoroalkyl substances (PFAS) by soybean and their effects on functional genes related to nitrification, denitrification, and nitrogen fixation

Here in this study, we set up a soil-microbe-soybean system spiked with PFOA, PFOS, or a PFAS mixture of eight PFAS and investigated the distribution of PFAS in the system and impacts on the abundance and expression level of genes involved in the nitrogen (N) cycle. When soybean was exposed to the PFAS mixtures, synergistic uptake by shoots was detected. PFAS exhibited remarkable impacts on abundance of nitrification and denitrification genes in both bulk soil and rhizosphere as well as expression of N fixation gene in soybean nodules. The abundance of nitrification genes AOA and AOB amoA and denitrification gene nirK was significantly reduced (p < 0.05) in almost all treatments in bulk soil, except PFOA at 10 μg/kg. The abundance of other functional genes, such as nirS and norZ was affected differently depending on PFAS concentrations and sample location, either bulk soil or the rhizosphere. Interestingly, the N fixation gene nifH in soybean nodules was overexpressed by a PFAS mixture at 100 μg/kg. Hence, this work provided in-depth knowledge regarding the distribution of PFAS and their impacts on the N cycle for the studied system. Results from this study provide insights on assessing risks posed by individual or mixed PFAS to soybean.

59 BASIC BIOLOGICAL SCIENCES↗