SEARCH · Engineering Papers
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
Materials for binding per- and polyfluoroalkyl substances (PFAS) are disclosed. A fluidic device comprising the materials for detection and quantification of PFAS in a sample is disclosed. The fluidic device may be configured for multiplexed analyses. Also disclosed are methods for sorbing and remediating PFAS in a sample. The sample may be groundwater containing, or suspected of containing, one or more PFAS.
Materials for binding per- and polyfluoroalkyl substances (PFAS) are disclosed. A fluidic device comprising the materials for detection and quantification of PFAS in a sample is disclosed. The fluidic device may be configured for multiplexed analyses. Also disclosed are methods for sorbing and remediating PFAS in a sample. The sample may be groundwater containing, or suspected of containing, one or more PFAS.
Recent drinking water regulations have imposed the need for per- and polyfluoroalkyl substances (PFAS) remediation. In response, treatment facilities may be required to retrofit existing treatment schemes to treat PFAS below maximum contaminant levels (MCLs). Adsorption technologies such as granular activated carbon (GAC) and ion exchange (IX) have been demonstrated to be effective; however, there are limited techno-economic metrics available which provide guidance on technology selection and design for diverse PFAS-containing source water conditions. Process systems engineering (PSE) tools which can traditionally perform these analyses are hindered by the data availability, model validity, and understanding of treatment phenomena for emerging contaminants. This work employs published data regressions, statistical models, process models, techno-economic analyses, and other process systems tools in a model-based uncertainty framework to consider the limitations of emerging contaminant research. Through this analysis framework, economic results are provided as probabilistic distributions based on the uncertainty of the models and diverse conditions that treatment facilities experience.
Approaches to tackle the wide and growing variety of highly persistent per- and polyfluoroalkyl substances (PFAS) are of pressing global need because of their detrimental human health effects, such as cancer, birth defects, and hormone imbalance. Sensitive, selective, and easy-to-use real-time sensors to monitor and detect PFAS and sorbents to extract them are critical to meeting government-mandated environmental concentrations. In this work, we combine all-atom molecular dynamics simulations, enhanced sampling, deep representational learning, and Bayesian optimization to perform high-throughput virtual screening for highly sensitive and selective molecular probes. Our molecular design space consists of 3850 linear hydrocarbon chains with varying degrees of halogenation with and without amine- and phosphine-based headgroups. By employing a data-driven search process, we efficiently explore the molecular design space to optimize the sensitivity to perfluorooctanesulfonic acid (PFOS) as a prototypical PFAS analyte and selectivity relative to a sodium dodecyl sulfate (SDS) interferent. We calculate 504 Gibbs free energies of probe-analyte and probe-interferent interactions and identify probes with PFOS association free energies of up to (-ΔG PFOS ) = 9.8 ± 0.2 kJ/mol and selectivities relative to SDS of (-ΔΔG PFOS–SDS ) = 3.1 ± 1.5 kJ/mol. A C 11 Br 23 P(CH 3 ) 2 probe containing 11 backbone brominated carbons and a tertiary phosphine headgroup possesses the most sensitive binding constant to PFOS within the defined search space of K b PFOS = 177.4 ± 12.7, and a semibrominated probe C 5 H 11 C 7 Br 14 N(CH 3 ) 2 containing 12 backbone carbons and a tertiary amine headgroup possesses the highest selectivity relative to SDS of K b PFOS /K b SDS = 4.6 ± 1.7. A retrospective analysis of our data to extract interpretable design rules reveals that the sensitivity of linear hydrogenated probes increases by approximately 1 kJ/mol per C–C bond. The addition or removal of halogen atoms and amine or phosphine headgroups produces nonmonotonic changes in both sensitivity and selectivity with changes to the sensitivity of up to 2.5 kJ/mol. Finally, this work places empirical limitations on the performance of a wide range of linear probes for PFOS detection and offers a generic strategy for high-throughput computational screening to promote selective and sensitive binding.
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.
Per- and polyfluoroalkyl substances (PFAS) are persistent environmental contaminants that resist conventional water treatment due to the strength of their carbon fluorine bonds. Electron-beam irradiation has shown potential for PFAS degradation; however, its effectiveness is limited by shallow energy penetration, restricting treatment to the upper region of the water surface. This project addresses this limitation through the design of a compact mixing chamber and recirculation system to enhance surface renewal and improve treatment efficiency. The system, constrained to approximately 10 cm 20 cm 20 cm, was developed using computer-aided design, computational fluid dynamics (CFD), and MATLAB-based hydraulic analysis to evaluate flow behavior, head loss, and pump compatibility. A perforated-baffle geometry and controlled flow range of 1 3 GPM were implemented to promote uniform mixing while maintaining a stable free surface for electron-beam exposure. Modeling results indicate improved flow distribution and reduced dead zones, supporting more consistent interaction between contaminated water and the beam. The final design enhances hydrodynamic performance within system constraints, contributing to scalable electron-beam water treatment technologies for improved PFAS degradation.
Black carbon-amended bioretention systems are an increasingly popular strategy for the removal of organic contaminants, including poly- and perfluoroalkyl substances (PFASs) and other trace organic contaminants (TOrCs), from urban stormwater. Many PFASs preferentially accumulate at the air–water interface, but detention time requirements for stormwater bioretention systems typically result in full saturation of the bioretention systems, effectively removing their air–water interfaces. This study assessed the effect of bioretention system saturation on removal of PFASs, metals, and hydrophilic TOrCs. A field-aged mixture of 40% v/v sand, 30% v/v zeolite, and 30% v/v biochar was packed into columns which were operated with hydraulic controls to remain unsaturated or fully saturated throughout the duration of the experiment. Twenty-four storm events sized to a 95th percentile storm at a California, United States military site were simulated using synthetic stormwater fortified with aqueous film forming foam-derived PFASs, TOrCs, and metals to mimic real-world conditions. Unsaturated conditions outperformed saturated conditions for removal of all PFASs analyzed. A simulated inadvertent system perturbation (i.e. flooding event) in the unsaturated columns did not result in significantly greater mobilization of PFAS mass, suggesting that more sorption to the biochar occurred as a result of the transient retention of PFASs at the air–water interface reducing kinetic sorption limitations. Overall, maintaining unsaturated conditions in a biofilter may extend the sorptive filter lifetime for PFASs by up to 83%. The results have implications for bioretention system application and design for PFAS removal in contaminated catchment areas.
Lowering per- and polyfluoroalkyl substances (PFAS) levels in the long term requires more than end-of-pipe treatment and expensive infrastructure upgrades. Here, a continuous-improvement framework can serve as a guide for active communication and engagement with upstream industrial dischargers. Measurement and monitoring, source reduction, management, and workforce development form essential pillars for effective PFAS management.
Per- and polyfluoroalkyl substances (PFAS) are a group of manufactured chemicals that have caught the attention of many governmental agencies and researchers. These chemicals are highly stable and possess hydrophobic properties that lead to the widespread use of PFAS in aqueous film forming foams, and household products such as carpets, paper and non-stick cookware (Prevedouros et al., 2006). Regulatory and health advisories have focused determining a lifetime drinking water health advisory of 70 ng/L for PFOA and PFOS (USEPA, 2016). Other PFASs may be present in the environment, along with PFOA and PFOS, due to product manufacturing processes (Prevedouros et al., 2006). A variety of proprietary AFFF formulations were manufactured and sold during different timeframes, thereby complicating the signature and distribution of PFASs in groundwater beneath former firefighting training areas (McGuire et al., 2014). PFOA and PFOS are stable chemicals that persistent in the environment and are difficult to remediate. The understanding of the physicochemical properties and fate and transport of PFASs in groundwater is growing but is still limited (USEPA, 2012). Many traditional approaches such as coagulation and conventional water treatment are ineffective in treating PFOA and PFOS. Selecting the most appropriate remedial strategy for PFOA and PFOS is therefore challenging. In this survey findings from the literature on PFASs removal using various technologies were compiled.
GenX, the trade name of hexafluoropropylene oxide dimer acid (HFPO-DA) and its ammonium salt, is a short-chain PFAS that has emerged as a substitute for the legacy PFAS perfluorooctanoic acid (PFOA). However, GenX has turned out to be more toxic than people originally thought. In order to monitor and regulate water quality according to recently issued drinking water standards for GenX, rapid and ultrasensitive detection of GenX is urgently needed. For the first time, this study reports ultrasensitive (as low as 1 part per billion (ppb)) and fast detection (in minutes) of GenX in water via surface-enhanced Raman spectroscopy (SERS) using a hierarchical nanofibrous SERS substrate, which was prepared by assembling ~60 nm Ag nanoparticles on electrospun nylon-6 nanofibers through a “hot start” method. The findings in this research highlight the potential of the engineered hierarchical nanofibrous SERS substrate for enhanced detection of short-chain PFASs in water, contributing to the improvement of environmental monitoring and management strategies for PFASs.
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.
Poster for concluding seed LDRD project on Moderate High Pressure X-ray Radiation-Induced Degradation of Persistent Poly- and Perfluoroalkyl Substances (PFAS). Project Number: 23P1-79-010FP.
Thousands of chemical contaminants threaten watersheds but are time and cost prohibitive to monitor. Identifying their sources, transport, and ecological risk is limited in heterogeneous urban watersheds. We present an integrative watershed approach using source-specific indicator compounds, common water quality measures, and ecotoxicity assays to examine the distribution of contaminant mixtures in an urbanized watershed. Indicator compound concentrations were temporally and spatially distributed for treated/untreated sewage (sucralose, artificial sweetener), road runoff (diphenyl-guanidine [DPG] and 6PPD-quinone [6PPD-Q], automobile tire additives), and lawncare runoff (aminomethanephosphonic acid (AMPA), major degradant of the herbicide glyphosate). Sucralose was predominately sourced from treated wastewater; measurable concentrations in tributaries indicated raw sewage inputs. DPG and 6PPD-Q concentrations correlated to road density during base flow and were elevated during stormflow. AMPA was measurable spring through fall, especially where lawns were dense. When specific sources dominated flow, water quality measures correlated with wastewater (sulfate, potassium, chloride, and sodium) and road runoff (chromium and lead) indicators. The limited behavioral toxicity observed in exposed zebrafish (Danio rerio) (18%) was not well explained by source-indicators. PFAS concentrations were highly variable spatially but not well explained by our source-specific indicator compounds. Here, more costly compound-specific monitoring may be necessary when multiple sources exist or when unexpected toxicity trends occur.
We have developed reaction libraries for predicting transformation products of PFAS in a variety of environmental and biological reaction systems.
Presentation discussing polyfluoroalkyl substances (PFAS) and their history, uses, impact on the environment, and proposals for treatment plans to reduce their presence in the environment.
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.
The designed e-beam irradiation beamline [1] at Jefferson Lab has been commissioned and applied to study the degradation removal of 1,4-dioxane and per- and polyfluoroalkyl substances (PFAS) in wastewater by collaborating with Hampton Roads Sanitation District (HRSD), treating wastewater in southeast Virginia. The absorbed dose and dose distribution in the entire sample were achieved innovatively using Monte-Carlo simulations that were calibrated with opti-chromic dosimeter rods directly exposed to the e-beam. This research could be a stepstone to the future MW compact SRF accelerator [2] for wastewater remediation.
This advanced technology involves the use of mesoporous carbon materials, which are modified with aliphatic quaternary amines to enhance their ability to capture and thermally degrade toxic per- and polyfluoroalkyl substance (PFAS) from water.