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At least 127 records · Page 7
All sourcesNASA NTRSDOE OSTI
DOE OSTI2021

Spatial and temporal baseline of perfluorooctanesulfonic acid retained in sediment core samples from Puget Sound, Washington, USA

Per- and poly-fluorinated alkyl substances (PFAS) are a group of highly persistent synthetic chemicals utilized in many industrial and consumer products, and — most significantly toward introduction to the marine environment — in fire-fighting foams. Recently, PFAS have been linked to adverse health effects, prompting the need to understand transport and fate. Puget Sound’s main basin, hosting densely populated urban and industrial areas, is known to be contaminated with various persistent organic pollutants and provides a central focus for ecosystem monitoring. Perfluorooctanesulfonic acid, a manufactured PFAS and biodegradation product, partitions to marine sediments and thus can be used as a primary indicator toward regulatory efforts. The current study offers a spatial and temporal analysis of the Puget Sound from cores collected adjacent, Tacoma and Seattle, WA, as well as cores from central Hood Canal and Carr Inlet.

Per- and poly-fluorinated alkyl substances (PFAS),↗
DOE OSTI2025

Sulfonated Diels–Alder Poly(Phenylene)s in Membrane Electrode Assemblies for Fuel Cells

The transition to environmentally sustainable materials in fuel cells requires alternatives to persistent polyfluoroalkyl substances (PFAS) like Nafion. This study investigates the performance-limiting factors of membrane electrode assemblies (MEAs) utilizing sulfonated Diels–Alder poly(phenylene)s (sDAPPs) as PFAS-free polymer electrolytes. Among the configurations evaluated, the greatest performance loss occurred when sDAPP is used as the cathode binder, primarily due to phenyl group adsorption on catalyst surfaces, which reduces oxygen reduction reaction activity and impedes oxygen transport. Additional performance degradation arises from membrane-electrode interfacial incompatibility and insufficient ionomer hydrophobicity. By addressing ionomer adsorption and improving interfacial contact, an sDAPP-based cathode achieved a current density of 1.57 A cm −2 at 0.6 V under fully humidified H 2 /air conditions at 80 °C and 150 kPa abs . These results offer key insights for advancing high-performance, PFAS-free fuel cell technologies.

08 HYDROGEN↗
DOE OSTI2026

Proton Conducting Silicon Oxide Membranes as a Fluorine Free Alternative to Nafion for Low Temperature Water Electrolysis

Driven by environmental and health concerns related to per- and polyfluoroalkyl substances (PFAS), there has been growing interest in developing fluorine-free proton (H + ) exchange membrane (PEM) materials for fuel cells and water electrolyzers. In this study, we present a side-by-side comparison of the key transport properties of submicron thick, PFAS-free amorphous silicon dioxide (SiO 2 ) membranes to Nafion, a fluorinated polymer electrolyte membrane that represents the industry standard for PEM fuel cells and electrolyzers. Here, measurements of proton (H + ) conductivity (σ H + ), hydrogen (H 2 ) permeability (P H 2 ), and electrical resistivity (ρ e – ) were conducted using model thin films comprised of SiO 2 membranes deposited by atomic layer deposition (ALD). Although the H + conductivity of the SiO 2 membranes is 2–3 orders of magnitude lower than Nafion, the addition of phosphorus dopants (PO x ) improves H + conductivity such that the area specific membrane resistance of thin (<50 nm) PO x -doped SiO 2 membranes is more than an order of magnitude lower than Nafion-117. Importantly, the safe operation of such nanoscale membranes within a PEM electrolyzer is feasible thanks to the low H 2 permeability of dense SiO 2 -based membranes, which are predicted to limit H 2 crossover rates to acceptable levels for pressures up to ≈ 100 bar. As a proof-of-principle demonstration, a chip-scale water electrolyzer based on 100 nm thick PO x -SiO 2 membrane is shown to achieve a current density of 2 A cm –2 at a potential of 2.5 V. If this technology can be successfully scaled up, H + conducting oxide membranes offer an attractive PFAS-free alternative to Nafion for efficient and durable water electrolysis and fuel cell technologies.

Nafion↗
DOE OSTI2026

Exploring Approaches for Accelerated Mass Spectrometric Detection of Fluorochemicals from Aqueous Solutions Using Indirect, Adsorbent-Facilitated Desorption Ionization

There is a growing need for rapid, low-cost analytical tools to screen water supplies for persistent contaminants. Due to their ubiquitous presence in the environment and their detrimental effects on human health, there is a public interest in widespread testing for perfluoroalkyl substances (PFAS). However, the most common methods for PFAS analysis can be time-intensive, requiring a preconcentration step followed by liquid chromatography–mass spectrometry (LC–MS), and are cost-prohibitive for most members of the public. To address these challenges, this study explores a novel method for rapid analysis of aqueous analytes by concentrating analytes on solid adsorbents and detecting them using mass spectrometric analysis via desorption ionization directly from the adsorbent surface. We demonstrate this general approach of indirect solution analysis (ISA) with desorption electrospray ionization (ISA-DESI) and laser desorption ionization (ISA-LDI). Various adsorbent materials were screened, including commercial mesoporous carbons, alumina, and metal–organic frameworks (MOFs). Using ISA-DESI, we consistently detect concentrations as low as 5–100 parts per trillion (ppt) for perfluorooctanoic acid (PFOA) and 10–100 ppt for perfluoroundecanoic acid (PFUnDA). This approach enables rapid detection in under 5 min, making it suitable for applications requiring trace detection with fast response times. We further demonstrate the use of ISA-DESI on a range of environmentally relevant contaminants. Advantages of this indirect solution analysis approach include simplified sample preparation, accelerated analysis, and low cost with readily available materials, making it a promising tool to accelerate mass spectrometric PFAS detection for identifying contaminated sites, performing laboratory studies, and monitoring industrial waste streams.

Bays, Nathan Robert [Sandia National Laboratories ↗
DOE OSTI2025

Reversible parts-per-trillion-level detection of perfluorooctane sulfonic acid in tap water using field-effect transistor sensors

Widespread, persistent and toxic per- and polyfluoroalkyl substances (PFAS) pose a major threat to water systems and human health. Current detection methods are relatively expensive, slow and complex, underscoring the need for more accessible alternatives to meet increasingly stringent PFAS regulations. Here, in this study, we present an ultrasensitive sensing platform for perfluorooctane sulfonic acid detection in tap water with a reporting limit ( ~ 250 parts per quadrillion) lower than the US Environmental Protection Agency’s regulatory standard (4 parts per trillion), using a remote gate field-effect transistor featuring β-cyclodextrin (β-CD)-modified reduced graphene oxide as the sensing membrane. The sensor exhibits excellent selectivity against common inorganic ions, natural organic matter and select organic pollutants in tap water. The reversible and rapid response ( < 2 min) indicates the potential of remote gate field-effect transistor for continuous in-line monitoring. Mechanistic studies using quartz crystal microbalance and molecular dynamics simulations reveal key roles of analyte adsorption and charge properties in sensing performance and offer insights for designing more selective PFAS capture probes.

Wang, Yuqin [University of Chicago, IL (United Sta↗
DOE OSTI2022

Low-temperature mineralization of perfluorocarboxylic acids

Per- and polyfluoroalkyl substances (PFAS) are persistent, bioaccumulative pollutants found in water resources at concentrations harmful to human health. Whereas current PFAS destruction strategies use nonselective destruction mechanisms, we found that perfluoroalkyl carboxylic acids (PFCAs) could be mineralized through a sodium hydroxide–mediated defluorination pathway. PFCA decarboxylation in polar aprotic solvents produced reactive perfluoroalkyl ion intermediates that degraded to fluoride ions (78 to ~100%) within 24 hours. The carbon-containing intermediates and products were inconsistent with oft-proposed one-carbon-chain shortening mechanisms, and we instead computationally identified pathways consistent with many experiments. Degradation was also observed for branched perfluoroalkyl ether carboxylic acids and might be extended to degrade other PFAS classes as methods to activate their polar headgroups are identified.

Science & Technology - Other Topics↗
DOE OSTI2025

Statistical Design of Experiments Enables Rapid Exploration of Perfluorobutane Sulfonate Degradation

The phase-out of long-chain PFAS has led to the proliferation of highly recalcitrant short-chain analogs, and mineralization technologies for these short-chain PFAS are needed to mitigate their deleterious effects on environmental and human health. In this study, we utilize a statistical design of experiments, specifically, response surface methodology, to rapidly evaluate the electrochemical degradation of the short-chain PFAS, perfluorobutane sulfonate (PFBS). We evaluate the impacts of the three primary electrochemical parameters (concentration of PFBS, concentration of supporting electrolyte, and applied current) over multiple orders of magnitude on the three primary reaction outcomes of electrochemical PFBS degradation (incomplete PFBS decomposition, complete PFBS mineralization as fluorine, and anodic energy consumption). Our results correspond with literature and clearly identify the well-known tradeoff between energy consumption and complete mineralization. Intriguingly, partial PFBS decomposition and energy consumption demonstrate nonlinear dependencies in the current/supporting electrolyte concentration space and the current/PFBS concentration space, respectively. These findings highlight the utility of the response surface methodology model to efficiently interrogate a large parameter space, identifying both common results and less-obvious interactions between electrochemical parameters and their influences on reaction outcomes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Critical Literature Review of Low Global Warming Potential (GWP) Refrigerants and their Environmental Impact

Refrigeration and air conditioning currently account for ~20% of the total electricity consumption in buildings around the world. Over the next three decades as global temperatures are projected to increase, urbanization and economic growth will lead to an increased demand for refrigeration and cooling. Most commonly used refrigerants belong to the five following classes: (i) chlorofluorocarbons, (ii) hydrochlorofluorocarbons, (iii) hydrofluorocarbons (HFCs), (iv) hydrofluoroolefins (HFOs), and (v) natural refrigerants. Over the past century, there have been shifts in which compounds were used for refrigeration to improve safety and durability, allow for ozone protection, and, most recently, to reduce global warming potential (GWP). Although technological advances have led to increased cooling capacity and safer refrigerants, emissions from refrigeration systems can affect the environment by contributing to greenhouse gas emissions or by depleting the ozone layer, depending on the gas emitted. The focus is increasingly on adopting compounds that are both efficient at cooling and effective for reducing emissions and other adverse environmental impacts. Because of policy and regulatory changes to avert ozone depletion and global climate change, much discussion has centered on the environmental impacts of next-generation refrigerants. Of particular interest are the fluorinated refrigerants, HFCs and HFOs, most of which are defined as per- and polyfluoroalkyl substances (PFAS) and their breakdown products (especially trifluoroacetic acid). The US Environmental Protection Agency in 2021 drafted a Strategic Roadmap for PFAS, which has already resulted in an increase in investment in research on these compounds and has restricted the release of PFAS into the environment through the implementation of monitoring and reporting requirements. A critical evaluation of fluorinated refrigerants and their breakdown products with respect to persistence, biodegradation and toxicity, and global warming potential is needed to guide environmental regulations. This document aims to perform a critical review of the relevant scientific data on the most common refrigerants currently used, their degradation products, and their alternatives. Where available, estimates of precursor production quantities and existing environmental regulatory information are reviewed. Key data of interest for the evaluation include physicochemical properties, environmental fate parameters, ecological or human health toxicity/risk information, and GWP for compounds of interest.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2024

Critical Literature Review of Low Global Warming Potential (GWP) Refrigerants and their Environmental Impact

Refrigeration and air conditioning currently account for ~20% of the total electricity consumption in buildings around the world. Over the next three decades as global temperatures are projected to increase, urbanization and economic growth will lead to an increased demand for refrigeration and cooling. Most commonly used refrigerants belong to the five following classes: (i) chlorofluorocarbons, (ii) hydrochlorofluorocarbons, (iii) hydrofluorocarbons (HFCs), (iv) hydrofluoroolefins (HFOs), and (v) natural refrigerants. Over the past century, there have been shifts in which compounds were used for refrigeration to improve safety and durability, allow for ozone protection, and, most recently, to reduce global warming potential (GWP). Although technological advances have led to increased cooling capacity and safer refrigerants, emissions from refrigeration systems can affect the environment by contributing to greenhouse gas emissions or by depleting the ozone layer, depending on the gas emitted. The focus is increasingly on adopting compounds that are both efficient at cooling and effective for reducing emissions and other adverse environmental impacts. Because of policy and regulatory changes to avert ozone depletion and global climate change, much discussion has centered on the environmental impacts of next-generation refrigerants. Of particular interest are the fluorinated refrigerants, HFCs and HFOs, most of which are defined as per- and polyfluoroalkyl substances (PFAS) and their breakdown products (especially trifluoroacetic acid). The US Environmental Protection Agency in 2021 drafted a Strategic Roadmap for PFAS, which has already resulted in an increase in investment in research on these compounds and has restricted the release of PFAS into the environment through the implementation of monitoring and reporting requirements. A critical evaluation of fluorinated refrigerants and their breakdown products with respect to persistence, biodegradation and toxicity, and global warming potential is needed to guide environmental regulations. This document aims to perform a critical review of the relevant scientific data on the most common refrigerants currently used, their degradation products, and their alternatives. Where available, estimates of precursor production quantities and existing environmental regulatory information are reviewed. Key data of interest for the evaluation include physicochemical properties, environmental fate parameters, ecological or human health toxicity/risk information, and GWP for compounds of interest.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2021

Photooxidative decomposition and defluorination of perfluorooctanoic acid (PFOA) using an innovative technology of UV–vis/Zn x Cu 1-x Fe 2 O 4 /oxalic acid

Per- and polyfluoroalkyl substances (PFAS) are a large group of perfluorinated organic molecules that have been in use since the 1940s for industrial, commercial, and consumer applications. PFAS are a growing concern because some of them have shown persistent, bioaccumulative and toxic effects. In this work, we demonstrate an innovative technology of UV–vis/Zn x Cu 1-x Fe 2 O 4 /oxalic acid for the degradation of perfluorooctanoic acid (PFOA) in water. The magnetically retrievable nanocrystalline heterogeneous ferrite catalysts, Zn x Cu 1-x Fe 2 O 4 were synthesized using a sol-gel auto-combustion process followed by calcination at 400 °C. The combination of Zn x Cu 1-x Fe 2 O 4 and oxalic acid generate reactive species under UV light irradiation. These reactive species are then shown to be capable of the photodegradation of PFOA. The degree of degradation is tracked by identifying transformation products using liquid chromatography coupled with quadrupole time-of-flight mass spectroscopy (LC-QTOF-MS).

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2024

Association Kinetics for Perfluorinated n -Alkyl Radicals

Radical-radical reaction channels are important in the pyrolysis and oxidation chemistry of perfluoroalkyl substances (PFAS). In particular, unimolecular dissociation reactions within unbranched n-perfluoroalkyl chains, and their corresponding reverse barrierless association reactions, are expected to be significant contributors to the gas-phase thermal decomposition of families of species such as perfluorinated carboxylic acids and perfluorinated sulfonic acids. Unfortunately, experimental data for these reactions are scarce and uncertain. Furthermore, obtaining reliable theoretical predictions for such reactions is a laborious and computationally intensive task. Here, in this work, the chemical kinetics of the various association/decomposition reactions producing/decomposing the C 2 -C 4 series of unbranched n-perfluoroalkanes (C 2 F 6 , C 3 F 8 , and C 4 F 10 ) are examined using state-of-the-art ab initio transition-state-theory-based master-equation calculations. The variable-reaction-coordinate transition-state theory (VRC-TST) formalism is employed in computing the microcanonical and canonical rates for the association reactions. Reaction thermochemistry is obtained via composite quantum chemistry calculations and the laddering of error-canceling reaction schemes via a connectivity-based hierarchy approach employing ANL1/ANL0-style reference energies. Lennard-Jones collision model parameters for the considered systems were estimated by a direct dynamics approach, and collisional energy transfer parameters were obtained from analogies to systems of similar size and heavy-atom connectivity. A one-dimensional master equation approach was used to convert the microcanonical rate coefficients from the VRC-TST analysis into temperature- and pressure-dependent rate constants for the association reactions and the reverse dissociation reactions. The data are reported in standardized formats for usage in comprehensive chemical kinetic models for PFAS thermal destruction.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Molecular detection of per- and polyfluoroalkyl substances in water using time-of-flight secondary ion mass spectrometry

Detection of per- and polyfluoroalkyl substances (PFASs) is crucial in environmental mitigation and remediation of these persistent pollutants. We demonstrate that time-of-flight secondary ion mass spectrometry (ToF-SIMS) is a viable technique to analyze and identify these substances at parts per trillion (ppt) level in real field samples without complicated sample preparation due to its superior surface sensitivity. Several representative PFAS compounds, such as perfluorooctanesulfonic acid (PFOS), perfluorobutanoic acid (PFBA), perfluoropentanoic acid (PFPeA), perfluoheptanoic acid (PFHpA), and perfluorononanoic acid (PFNA), and real-world groundwater samples collected from monitoring wells installed around at a municipal wastewater treatment plant located in Southern California were analyzed in this work. ToF-SIMS spectral comparison depicts sensitive identification of pseudo-molecular ions, characteristic of reference PFASs. Additionally, principal component analysis (PCA) shows clear discrimination among real samples and reference compounds. Our results show that characteristic molecular ion and fragments peaks can be used to identify PFASs. Furthermore, SIMS two-dimensional (2D) images directly exhibit the distribution of perfluorocarboxylic acid (PFCA) and PFOS in simulated mixtures and real wastewater samples. Such findings indicate that ToF-SIMS is useable to determine PFAS compounds in complex environmental water samples. In conclusion, ToF-SIMS provides simple sample preparation and high sensitivity in mass spectral imaging, offering an alternative solution for environmental forensic analysis of PFASs in wastewater in the future.

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

Silylsilane‐Substituted Polymers: Fluorine‐Free, Liquid Repellent, and Hydrolytically Stable Alternatives to Siloxanes

Abstract Per‐ and polyfluoroalkyl substances (PFAS) are omniphobic and exceptionally stable, making them ideal for a wide range of materials applications. However, as “forever chemicals”, their exceptional persistence and bioaccumulation have generated an increasing amount of environmental and health concerns, prompting the search for fluorine‐free alternatives. Siloxane‐based materials are therefore interesting to examine as PFAS alternatives due to their low surface energy and hydrophobicity but suffer from hydrolytic instability of Si─O linkages. To address this challenge, a novel methacrylate monomer, 3‐[tris(trimethylsilyl)silyl]propyl methacrylate (M‐silyl), is designed containing Si─Si bonds rather than Si─O bonds of siloxanes. Polymers derived from M‐silyl (P‐silyl) is prepared by controlled free radical polymerization and compared with their siloxane analogues after coating on silicon wafers. Contact angle (CA) measurements confirmed P‐silyl to be hydrophobic (advancing/receding water CA = 109.7°/83.0°), with a low‐hysteresis for oil (lyophobic) (hexadecane CA hysteresis = 2.0°), comparable to its siloxane‐based counterpart. Importantly, P‐silyl maintained these surface properties after exposure to acidic or basic conditions, while siloxane analogues lost hydrophobicity. Consequently, the incorporation of Si ─ Si linkages into the design of the polymer enables chemically stable, fluorine‐free alternatives for water‐repellent and low hysteresis surface coatings and advances the design of fluorine‐free functional materials.

fluorine-free↗
DOE OSTI2026

Stereochemically‐Controlled Fluorinated Copolymers for Selectively Permeable Barrier Applications

Selective oxygen permeability coupled with low water vapor transmission is essential for biomedical and packaging applications requiring controlled oxygen flux under humid conditions. However, most high‐performance barrier polymers depend on perfluoroalkyl substances (PFAS), whose persistence and regulatory restrictions limit their long‐term applicability. We designed a series of stereocontrolled thiol‐yne‐based polyesters, including both fluorinated and non‐fluorinated variants, for selective oxygen permeability with considerable water barrier performance. Tailoring polymer crystallinity and morphology tuned both oxygen transport and mechanical properties. Fluorinated polymers demonstrated enhanced hydrophobicity and water resistance while maintaining oxygen diffusivity within a range relevant to oxygen‐sensing applications. Structure–property relationships were elucidated through small‐ and wide‐angle X‐ray scattering, revealing semi‐crystalline domains influenced by fluorine content and dithiol chain length. Barrier performance was rigorously evaluated via water vapor transmission rate and dynamic vapor sorption, showing reduced water uptake with increasing dithiol monomer length and crystallinity. In conclusion, this work introduces a PFAS‐free alternative to conventional barrier materials and establishes a tunable materials platform with potential relevance for biomedical devices and packaging systems requiring controlled oxygen permeability.

36 MATERIALS SCIENCE↗
DOE OSTI2026

Adsorption-Engineered Hydrocarbon Ionomers for Durable Proton-Exchange Membrane Fuel Cells

Reducing reliance on perfluoroalkyl substances (PFAS) in proton-exchange membrane fuel cells requires hydrocarbon ionomers that combine high performance with long-term durability, a persistent challenge in catalyst-layer design. Here, we identify oxidation-driven ionomer-catalyst interfacial degradation as a dominant failure pathway in hydrocarbon ionomer-bonded cathodes and introduce an adsorption-engineering strategy to overcome this limitation. The comparison of a commercial sulfonated poly(phenylene) (Pemion) with structurally engineered sulfonated poly(fluorene)s demonstrated that electrode durability is governed by the interplay between ionomer adsorption strength and resistance to oxidative degradation on carbon-supported Pt catalysts. A poly(fluorene) ionomer with mobile alkyl sulfonic acid groups forms resilient interfaces, delivering 1.28 A cm−2 at 0.65 V under fully humidified H2/air conditions (80°C and 150 kPaabs), comparable to Pemion. After 90,000 accelerated potential cycles, the poly(fluorene)-bonded cathode exhibits significantly improved durability, with only 29% performance loss compared to 58% for Pemion; further molecular refinement reduces the loss to 17%, approaching that of Nafion-bonded cathodes (14%). These findings establish adsorption-engineered ionomer design that decouples interfacial anchoring from oxidative degradation as a general strategy for achieving durable, high-performance PFAS-free PEM fuel cell electrodes.

08 HYDROGEN↗
DOE OSTI2026

Covalent adaptable networks for electrolyte–binder integration in recyclable lithium metal batteries

Lithium-metal batteries (LMBs) are considered a promising next-generation energy storage technology due to their exceptionally high energy density. However, the development of solid polymer electrolytes and cathode binders for LMBs faces critical challenges, including interfacial instability, poor recyclability, and growing environmental concerns. In particular, current systems often rely on non-recyclable components featuring permanently crosslinked networks and polyfluoroalkyl substances (PFAS), such as poly(vinylidene fluoride) (PVDF), which cause battery waste and environmental harm. Herein, we introduce a multifunctional covalent adaptable network (CAN) platform based on thermally reversible Diels–Alder (DA) chemistry, designed for dual functionality as a CAN-based electrolyte (CAE) and a CAN-based cathode binder. The CAE achieves high ionic conductivity and strong storage modulus (1.4 mS cm −1 and ∼ 10 5 Pa at room temperature, respectively) and enables stable long-term cycling in symmetric Li||Li cells for over 2000 h with low overpotential. When it is applied as a cathode binder in LiFePO 4 (LFP) composite electrodes (C-LFP), the CAN matrix significantly reduces interfacial resistance and enhances discharge capacity compared to conventional PVDF-based systems. Thermal treatment induces self-healing at the cathode–electrolyte interface, further improving contact and yielding a discharge capacity of 150 mAh g −1 at 0.5 C. Moreover, the dynamic CAN architecture allows efficient recovery and reuse of lithium salts from spent electrolytes through retro-DA reactions under mild conditions (∼80 °C), establishing a low-energy, cost-effective recycling pathway. In conclusion, this work presents a scalable and sustainable strategy for high-performance LMBs by integrating recyclability, interfacial healing, and PFAS-free design, offering a holistic solution aligned with circular economy principles and next-generation battery demands.

Diels–Alder↗
DOE OSTI2021

Prenatal exposure to mixtures of persistent endocrine disrupting chemicals and postnatal body size in British girls

Endocrine disrupting chemical (EDC) exposure is ubiquitous. EDC exposure during critical windows of development may interfere with the body's endocrine system, affecting growth. Previous human studies have examined one EDC at a time in relation to infant growth. By studying mixtures, the human experience can be better approximated. We investigated the association of prenatal exposure to persistent EDCs (per- and polyfluoroalkyl substances (PFAS), polychlorinated biphenyls (PCBs), and organochlorine pesticides (OCPs)) as mixtures with postnatal body size among female offspring. We used a sub-sample of the Avon Longitudinal Study of Parents and Children (N = 425), based in the United Kingdom. We quantified 52 EDCs in maternal serum collected during pregnancy. We used Bayesian kernel machine regression with a random intercept to examine the association of prenatal concentrations of EDC mixtures with longitudinal postnatal body size measures for each EDC class separately (PFAS, PCBs, and OCPs) and for all three classes combined. Weight and height measures at 0, 2, 9, and 19 months were obtained by health professionals as part of routine child health surveillance. The mixture representing all three classes combined (31 chemicals) (n = 301) was inversely associated with postnatal body size. Holding all EDCs in the 31-chemical mixture at the 75th percentile compared to the 50th percentile was associated with 0.15 lower weight-for-age z-score (95% credible interval –0.26, –0.03). Weak inverse associations were also seen for height-for-age and body mass index-for-age scores. Furthermore, these results suggest that prenatal exposure to mixtures of persistent EDCs may affect postnatal body size.

59 BASIC BIOLOGICAL SCIENCES↗
DOE OSTI2023

Linkage Transformations in a Three-Dimensional Covalent Organic Framework for High-Capacity Adsorption of Perfluoroalkyl Substances

Despite their many advantages, covalent organic frameworks (COFs) built from three-dimensional monomers are synthetically difficult to functionalize. Herein, we provide a new synthetic approach to the functionalization of a three-dimensional covalent organic framework (COF-300) by using a series of solid-state linkage transformations. By reducing the imine linkages of the framework to amine linkages, we produced a more hydrolytically stable material and liberated a nucleophilic amino group, poised for further functionalization. We then treated the amine-linked COF with diverse electrophiles to generate a library of functionalized materials, which we tested for their ability to adsorb perfluoroalkyl substances (PFAS) from water. The framework functionalized with dimethylammonium groups, COF-300-dimethyl, adsorbed more than 250 mg of perfluorooctanoic acid (PFOA) per 1 g of COF, which represents an approximately 14,500-fold improvement over that of COF-300 and underscores the importance of electrostatic interactions to PFAS adsorption performance. In conclusion, this work provides a conceptually new approach to the design and synthesis of functional three-dimensional COFs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗