Perfluoroalkyl Substances Research Articles

Making Waves: The Progress of Management Strategies for Cleaning and Rinsing of PFAS-Impacted Fire Suppression Systems

Aircraft rescue firefighting (ARFF) vehicles often contain residual levels of per- and polyfluoroalkyl substances (PFAS) due to the global use of legacy and current use of aqueous film-forming foam (AFFF) for class B firefighting. However, numerous countries are transitioning to fluorine-free foam (F3) alternatives. There is, thus, an urgent need to develop efficient methods to rinse and clean interior ARFF surfaces thereby avoiding expensive replacement costs and preventing further discharge of PFAS to the environment. However, the unique self-assembly behavior of amphiphilic PFAS is a complicating factor that can result in measurable levels of PFAS within replacement F3s following cleanout efforts (i.e., the rebound effect). This Making Waves article aims to elucidate the emerging challenges associated with cleanout of impacted ARFF vehicles and introduce the current efforts for PFAS management of rinsate derived from cleanout of impacted fire suppression infrastructure.

Serum levels of per- and poly-fluoroalkyl substances among middle-aged and elderly populations in Beijing and their association with dyslipidemia

Per- and poly-fluoroalkyl substances (PFAS), ubiquitous environmental pollutants, have been reported as possible contributors to human dyslipidemia. However, evidence for emerging PFAS remains scarce. Using a nested case-control study (n = 357) in a middle-aged and elderly population from Beijing, we investigated the serum concentrations of eight traditional and fourteen emerging PFAS and their potential links with dyslipidemia. Perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) were found to be the dominant PFAS. Serum levels of perfluorohexanesulfonic acid (PFHxS) and 6:2 chlorinated polyfluoroalkyl ether sulfonate (6:2 Cl-PFESA/F53B) were associated with higher risk of elevated low-density lipoprotein cholesterol (LDL-C) with odds ratios (OR) of 3.88 (95% CI: 1.44–10.51) and 2.71 (95% CI: 1.11–6.57), respectively. These compounds also positively correlated with high total cholesterol (TC). PFOA, perfluorodecanoic acid (PFDA), and 6:2 Fluorotelomer phosphate monoester (6:2 PAP) were linked to increased risk of high triglycerides (TG) with OR of 2.79 (95% CI: 1.30–6.01), 2.41 (95% CI: 1.27–4.60), and 1.53 (95% CI: 1.05–2.22), respectively. Conversely, perfluorooctane sulfonamidoacetic acid (FOSAA) was negatively associated with high TG levels. These findings indicate that both traditional and emerging PFAS may induce dyslipidemia, emphasizing the potentially serious impact of emerging PFAS on human health.

Legacy and emergent contaminants in glaucous-winged gull eggs from Canada's Pacific coast: Spatial distribution, temporal trends, and risks for human consumers

Using glaucous-winged gull (Larus glaucescens) eggs from Canada's Pacific coast, we investigated spatial and temporal trends (2008–2022) of a suite of legacy and emergent contaminants, including 16 perfluoroalkyl substances (PFAS), 15 polybrominated diphenyl ethers (PBDEs), 7 alternative halogenated flame retardants (AHFRs), total mercury (THg), as well as stable isotopes of carbon (δ13C) and nitrogen (δ15N) to control for diet. Legacy organochlorines (OCs) were also measured in eggs in 2020 for a preliminary human health risk assessment (HHRA). Between 2008 and 2022, glaucous-winged gull eggs from more urban-influenced colonies (Mandarte Island) were up to ∼2x more contaminated with PFAS, PBDEs, AHFRs, and THg than eggs from the offshore colony (Cleland Island), suggesting different source regions and dietary exposures. Concentrations of Σ15PBDEs declined linearly among colonies (p < 0.001), consistent with several North American phase-outs and regulatory restrictions dating back to the early/mid 2000s. Conversely, temporal trends for PFOS, Σ12PFCAs, Σ7AHFRs, and THg were characterized by a combination of second-order declines and non-linear increases in recent years. After correcting THg for dietary shifts using δ15N, THg concentrations followed a U-shaped trend at Mandarte and Cleland Islands, while those at Mitlenatch Island remained relatively constant over time. Increasing trends for some contaminants coincided with both an increase in δ13C and δ15N. For the HHRA, all gull eggs collected in 2020 had hazard quotients (HQs) < 0.2, indicating no foreseeable risk or harm for First Nations consumers for certain contaminants. Our findings indicate that spatio-temporal trends of persistent organic contaminants and THg in Pacific glaucous-winged gull eggs are influenced by a combination of factors, including the impact of regulations on anthropogenic emissions, accompanied by changes in foraging behaviour and food-web structure.

E-waste in the environment: Unveiling the sources, carcinogenic links, and sustainable management strategies

E-waste refers to electrical and electronic equipment discarded without the intent of reuse by choice or at the end of its functional lifespan. In 2022, approximately 62 billion kilograms of e-waste, equivalent to 7.8 kilograms per capita, was generated globally. With an alarming annual growth of approximately 2 million metric tonnes, e-waste production may exceed 82 billion kilograms by 2030. Improper disposal of e-waste can be detrimental to human health and the entire biosphere. E-waste encompasses a wide range of chemicals, including heavy metals, Polychlorinated Biphenyls (PCBs), Per- and Polyfluoroalkyl Substances (PFAS), Polycyclic Aromatic Hydrocarbons (PAHs), Polychlorinated Dibenzo-dioxins and -furans (PCDD/Fs), Polybrominated Diphenyl Ethers (PBDEs), and radioactive elements. Improper disposal of e-waste equipment can directly contaminate the aquatic and terrestrial environment, leading to human exposure through ingestion, inhalation, dermal absorption, and trans-placental transfer. These contaminants can directly enter the human body from the environment, potentially fueling carcinogenesis by modulating cell cycle proteins, inducing oxidative stress, and mutations. Heavy metals such as cadmium, mercury, arsenic, lead, chromium, and nickel along with organic pollutants like PAHs, PCBs, PBDEs, PFAS, and radioactive elements, play a crucial role in inducing malignancy in humans. Effective collection, sorting, proper recycling, and appropriate disposal techniques are essential in reducing environmental contamination by e-waste-derived chemicals. Hence, this comprehensive review aims to uncover the global environmental burden of e-waste and its links to carcinogenesis in humans. Furthermore, it provides an inclusive discussion on potential treatment approaches to minimize environmental e-waste contamination.

Non-extractable residues of perfluorooctanoic acid (PFOA) in soil

Perand polyfluoroalkyl substances have gained increased attention due to their persistence, ubiquitous presence in the environment, and toxicity. We hypothesised that the formation of non-extractable residues [NER] occurs in soils and contributes to the overall persistence of these priority pollutants, and that NER formation is controlled by temperature. To test these hypotheses, we used 14C-labelled perfluorooctanoic acid [PFOA] as target compound, added it to two arable soils (Cambisol, Luvisol), and incubated them at 10°C and 20°C in the dark. To support potential co-metabolic decomposition, some samples were additionally fed with glucose to enhance microbial activity. The PFOA residues were then sequentially extracted using 0.01 M CaCl2, followed by accelerated solvent extraction (ASE) with methanol or methanol/acetic acid after 0, 1, 3, 9, 30, 62, and 90 days of incubation. In addition, we monitored the release of 14C into the gas phase as well as [14C]-PFOA-NER after dry combustion and liquid scintillation counting. After 90 days, we found that the [14C]-PFOA content declined in the extraction order of CaCl2 ((bio)available fraction) > ASE (residual fraction) > NER > gas fraction), with most rapid changes occurring in the first 9 days of incubation. NER formation was different in the two soils and reached 5-9% of the applied amount in the Cambisol and Luvisol, respectively. Noteworthy the proportion of 14C-PFOA in the (bio)available fraction remained relatively stable over time at 56-62% of the applied amount, indicating the reversible transfer into this fraction from a bi-exponentially declining residual (ASE) pool. These dissipation patterns were neither influenced by temperature nor by the addition of glucose. We conclude that NER exist for PFOA, but that the majority of PFOA remains in (bio)available form, thus maintaining toxicity and mobility in soil for prolonged periods of time.

In Vitro Per- and Polyfluoroalkyl Substances (PFAS) Adsorption Assessment through Mesoporous Styrene-Divinylbenzene Sorbent Cartridge

In Vitro Per- and Polyfluoroalkyl Substances (PFAS) Adsorption Assessment through Mesoporous Styrene-Divinylbenzene Sorbent Cartridge

The influence of functional groups on the pyrolysis of per- and polyfluoroalkyl substances

Thermal treatment is a widely used remediation strategy for PFAS-contaminated materials such as soil, spent sorbents, and domestic waste. To better understand the effectiveness and environmental impact of thermal treatments for PFAS-contaminated materials, a fundamental understanding of PFAS thermal degradation mechanisms is required. This work aims to study the pyrolysis of six representative PFAS compounds, all of which have an eight-carbon length but with different functional groups. To assess the thermal stability and pyrolysis products of these six PFAS compounds, evolved gas analysis (EGA) was performed using thermogravimetric analysis/differential scanning calorimetry (TGA/DSC) coupled with an infrared spectrometer (IR) and a mass spectrometer (MS), as well as pyrolysis-GCMS (Pyr-GCMS). The EGA data demonstrates that compounds with lower estimated vapor pressures were generally found to be more thermally labile, and the presence of an ionic bond necessitates higher temperatures for pyrolysis. Pyrolysis at 900 °C yielded a variety of fluorinated organic compounds at significant signals. Tetrafluoroethene constituted the majority of the Pyr-GCMS signal for all the compounds. Moreover, a significant fraction of detected products was unable to be identified, underscoring a need for better tools to help with the identification of unknowns. Pyrolysis can occur through random chain scission, scission of the functional group, scission of the terminal CF3 group, and HF elimination. Some compounds may undergo more complete beta-scission to produce smaller pyrolysis products compared to others. The presence of acidic protons within the functional group can help facilitate HF elimination, whereas the salt form of a PFAS compound is less likely to undergo HF elimination. Termination of radical intermediates can either be recombination with a CF3 radical or hydrogen abstraction (H-abstraction). Observed hydrogen-substituted products indicate that functional groups with higher hydrocarbon character may lead to more H-abstraction terminated products. Overall findings show that the functional group of a PFAS may decrease or increase its thermal stability and lead to different profiles of pyrolysis products.

Removal of per- and polyfluoroalkyl substances (PFAS) from municipal wastewater by foam fractionation

Removal of per- and polyfluoroalkyl substances (PFAS) from municipal wastewater by foam fractionation

Enhanced selective photocatalytic reduction and oxidation of perfluorooctanoic acid on Bi/Bi5O7I decorated with poly (triazine imide)

Perfluorooctanoic acid (PFOA) is detected widely in surface and groundwater globally. Its removal poses a significant challenge due to its high chemical stability. This study demonstrates efficient PFOA degradation using poly-triazine-imides-tailored defective Bi5O7I (PTI/BB). Under 300W Xe irradiation, 1µg·L-1 PFOA could be degraded to 9.86ng·L-1 after 3hours in the presence of 0.5g·L-1 25% PTI/BB. The mechanism investigation reveals that the oxygen vacancy (OV) in partially reduced Bi/Bi5O7I (BB) generates impurity states, enhancing the light-harvesting capacity. Furthermore, forming a type Ⅱ heterojunction between conjugated PTI and BB facilitates the efficient separation of photogenerated carriers. The resulting photogenerated electrons (reduction) and holes (oxidation) drive hydrogenation reduction and oxidative decarboxylation of PFOA, respectively. This synergistic effect consequently achieves significant defluorination of PFOA. The proposed PFOA degradation pathway via the PTI/BB catalyst offers new insights into the catalyst design for photocatalytic degradation of per- and polyfluoroalkyl substances (PFAS).

Effect of high-frequency ultrasonication on degradation of polytetrafluoroethylene (PTFE) microplastics/nanoplastics

Polytetrafluoroethylene (PTFE) particle might present a significant contamination in environment due to its dual classification as a microplastic and a fluorinated compound (a type of PFAS, or per- and polyfluoroalkyl substances), coupled with its extreme stability. Identifying an effective degradation method for PTFE microplastics is thus crucial towards remediation, along with the suitable monitoring approaches. This study is the first to use high-frequency (580 kHz) ultrasonication for the degradation of the PTFE microplastics with diameter of ∼1000 nm. Dispersion of PTFE microplastics with help of surfactant (SDS, or sodium dodecyl sulfate) followed by ultrasonication for 9 h under optimal conditions resulted in a defluorination percentage of ∼32 %. Particle size analysis demonstrated the effective diameter shrink of PTFE microplastics by ultrasonication (from ∼1000 nm to ∼330 nm that can be categorized as nanoplastics). SEM-EDS provided clear visualization of PTFE microplastics/nanoplastics, while Raman imaging confirmed the fine particles from molecular spectrum window. ImageJ analysis algorithms were utilized to estimate particle sizes as well. Based on these findings, a potential degradation mechanism for PTFE microplastics/nanoplastics was proposed. This study contributes to the understanding of PTFE degradation and may facilitate further research in this field.

Combined environmental relevant exposure to perfluorooctanoic acid and zinc sulfate enhances apoptosis through binding with endogenous antioxidants in Daphnia magna

Perfluorooctanoic acid (PFOA) is a long-chain legacy congener of the per- and polyfluoroalkyl substances (PFAS) family, notorious as a "forever chemical" owing to its environmental persistence and toxic nature. Essential elements such as zinc (Zn) can cause toxic effects when they change their metal speciation and become bioavailable, such as zinc sulphate (ZnSO4). Combined toxicity assessment is a realistic approach and a challenging task to evaluate chemical interactions and associated risks. Therefore, the present study aims to elucidate the acute mixture toxicity (12–48 hours) of PFOA and ZnSO4 in Daphnia magna at environment-relevant concentrations (ERCs, low dose: PFOA 10 μg/L ZnSO4 20 μg/L; high dose: PFOA 20 μg/L ZnSO4 50 μg/L) in terms of developmental impact, apoptosis induction, and interaction with major endogenous antioxidants. Our results showed that deformity rates significantly increased (p < 0.05) with increasing exposure duration and exposure concentrations, compared to the control group. Further, lack of antenna, tale degeneration, and carapace alterations were the most commonly observed deformities following combined exposure to PFOA and ZnSO4, and these malformations were particularly pronounced after 48 h of exposure. Acridine orange (AO) staining was employed to examine apoptosis in D. magna, and apoptotic cells in terms of bright green fluorescence were detected in the abdominal claw carapace, heart, and post-abdominal area following exposure to a high dose of PFOA and ZnSO4. The molecular docking results revealed that both PFOA and ZnSO4 showed strong binding affinities with endogenous antioxidants CAT and GST, where PFOA was more strongly bound with CAT and GST with higher docking scores of -9.59 Kcal/mol and -7.49 Kcal/mol than those with ZnSO4 (-6.70 Kcal/mol and -6.55 Kcal/mol, respectively). In conclusion, the mixture exposure to PFOA and ZnSO4 at the environmental level induce developmental impacts and apoptosis through binding with major endogenous antioxidants in D. magna.

A novel high-throughput quantitative method for the determination of per- and poly-fluoroalkyl substances in human plasma based on UHPLC-Q/Orbitrap HRMS coupled with isotope internal standard

A novel high-throughput quantitative method for the determination of per- and poly-fluoroalkyl substances in human plasma based on UHPLC-Q/Orbitrap HRMS coupled with isotope internal standard

Transition-metal-free defluorinative cyclization of perfluoroalkyl alkenyl iodides with C,N-dinucleophiles: Synthesis of (E)-perfluoroalkenyl pyrroles

Functionalization of the C-F bond in perfluoroalkyl substances represents an emerging focus in organic chemistry. We report here a transition-metal-free intermolecular defluorinative cyclization of perfluoroalkyl alkenyl iodides with C,N-dinucleophiles. This method enables highly chemo-, regio-, and stereoselective 2-fold C (sp3)-F bond cleavage at two vicinal carbon centers in the perfluoroalkyl chain, resulting in the assembly of a five-membered N-heterocycle with a structurally privileged (E)-prefluoroalkenyl unit. The success of partial defluorination is mainly attributed to the pre-installed alkenyl functionality and iodide atom in perfluoroalkyl substances.

Integration of vacuum UV/peroxydisulfate and reductive processes for the thorough defluorination of 8:3 fluorotelomer carboxylates: The critical contribution of preoxidation

Fluorotelomers have been systematically developed in bulk quantities and extensively applied in the fluoropolymer industry. Reductive treatments of fluorotelomers are different from those of perfluoroalkyl substances. In this study, vacuum UV/peroxydisulfate (VUV/PDS) was used for the first time to preoxidize 8:3 fluorotelomer carboxylates (8:3FTCA). Subsequently, it was integrated with the VUV/sulfite/iodide reductive process to accomplish the comprehensive defluorination of the oxidized products. The performance and mechanisms of 8:3FTCA degradation in the preoxidation process were mainly explored. pH values from 6.0 to 8.0 were conducive to 8:3FTCA decomposition. Hydrogen peroxide, hydroxyl radical (•OH), and hydroperoxyl radical (HO2•) were observed to be in a dynamic equilibrium state of mutual transformation, and the contributions of •OH and HO2• were 76.8 % and 17.4 %, respectively. The investigation of the influences of background water matrices demonstrated minimal adverse effects of sulfate and chloride, whereas bicarbonate, carbonate, and natural organic matter exhibited inhibitory effects. The degradation pathways of 8:3FTCA were speculated through density functional theory calculation and intermediate identification. The Ecological Structure–Activity Relationships simulation showed that VUV/PDS preoxidation decreased the aquatic toxicity of 8:3FTCA. These findings provide valuable insights for addressing challenges associated with fluorotelomer carboxylates.

Association of perfluoroalkyl substances (PFAS) with liver function biomarkers in the highly exposed population of the veneto region

IntroductionEpidemiological studies highlight the presence of associations between per- and polyfluoroalkyl substances (PFAS) exposure with liver damage. In 2013, PFAS contamination was discovered in Veneto (Italy), leading to the implementation of a Surveillance Program (SP). Our objective is to investigate the association between PFAS exposure and biomarkers of liver function using single-pollutant and mixture approaches, while exploring the sex-specific differences and the mediating role of obesity in the association. MethodsThe study included 42,094 subjects aged ≥20 years participating in the SP. We used generalized additive models to investigate the association between several PFAS and alanine aminotransferase (ALT) and aspartate aminotransferase (AST) levels, adjusting for possible confounders and stratifying by sex. Results were back-transformed to show predicted percentage changes in outcomes per ln-unit increase in PFAS levels; furthermore, we explored the role of BMI in the abovementioned causal pathway, considering it as a potential confounder or mediator PFAS joint effect was investigated using Quantile G-computation. ResultsOne ln-unit increase in PFHxS concentrations was associated with a 1.49% (95%CI: 0.87, 2.12) and a 0.84% (95% CI: 0.27, 1.40) increase in ALT levels, in males and females respectively; one ln-unit increase in PFOA concentrations was associated with a 1.03% (95%CI: 0.50, 1.55) increase in ALT levels in males, and a 0.52% (95% CI: 0.22, 0.82) and a 0.60% (95% CI: 0.25, 0.96) increase in AST levels in females and males. PFOS showed no association with ALT and AST levels. Quantile G-computation revealed that an interquartile increase in the PFAS mixture was associated with a 3.02% increase (95% CI: 1.65, 4.43) and a 1.65% (95% CI: 0.77, 2.5) increase in ALT levels, in females and males. Mediation analysis suggested that BMI suppressed the association between PFAS and ALT levels, with positive direct effects higher than the total effects. ConclusionOur findings suggest sex-specific associations between PFAS exposure and liver function biomarkers and underscore the need for additional studies on potential mediators.

Tissue distribution and temporal and spatial assessment of per- and polyfluoroalkyl substances (PFAS) in smallmouth bass (Micropterus dolomieu) in the mid-Atlantic United States

Per- and polyfluoroalkyl substances (PFAS) have become an environmental issue worldwide. A first step to assessing potential adverse effects on fish populations is to determine if concentrations of concern are present in a region and if so, in which watersheds. Hence, plasma from adult smallmouth bass Micropterus dolomieu collected at 10 sites within 4 river systems in the mid-Atlantic region of the United States, from 2014 to 2019, was analyzed for 13 PFAS. These analyses were directed at better understanding the presence and associations with land use attributes in an important sportfish. Four substances, PFOS, PFDA, PFUnA, and PFDoA, were detected in every plasma sample, with PFOS having the highest concentrations. Sites with mean plasma concentrations of PFOS below 100 ng/ml had the lowest percentage of developed landcover in the upstream catchments. Sites with moderate plasma concentrations (mean PFOS concentrations between 220 and 240 ng/ml) had low (< 7.0) percentages of developed land use but high (> 30) percentages of agricultural land use. Sites with mean plasma concentrations of PFOS > 350 ng/ml had the highest percentage of developed land use and the highest number PFAS facilities that included military installations and airports. Four of the sites were part of a long-term monitoring project, and PFAS concentrations of samples collected in spring 2017, 2018, and 2019 were compared. Significant annual differences in plasma concentrations were noted that may relate to sources and climatic factors. Samples were also collected at two sites for tissue (plasma, whole blood, liver, gonad, muscle) distribution analyses with an expanded analyte list of 28 PFAS. Relative tissue distributions were not consistent even within one species of similar ages. Although the long-chained legacy PFAS were generally detected more frequently and at higher concentrations, emerging compounds such as 6:2 FTS and GEN X were detected in a variety of tissues.

Eco-environmental responses of Eichhornia crassipes rhizobacteria community to co-stress of per(poly)fluoroalkyl substances and microplastics

The stabilization of rhizobacteria communities plays a crucial role in sustaining healthy macrophyte growth. In light of increasing evidence of combined pollution from microplastics (MPs) and per- and polyfluoroalkyl substances (PFASs), Selecting typical floating macrophyte as a case, this study explored their impacts using hydroponic simulations and 16S rRNA high-throughput sequencing. A total of 31 phyla, 77 classes, 172 orders, 237 families, 332 genera, and 125 rhizobacteria species were identified. Proteobacteria (16.19% to 57.70%) was the dominant phylum, followed by Bacteroidota (12.34% to 44.48%) and Firmicutes (11.31% to 36.36%). In terms of α-diversity, polystyrene (PS) MPs and PFASs significantly impacted community abundance (ACE and PD-tree) rather than evenness (Shannon and Pielou) compared to the control. βMNTD and βNTI analyses revealed that PS MPs enhanced deterministic assembly processes driven by F-53B and GenX, while mitigating those induced by PFOA and PFOS. Contamination treatments narrowed the ecological niche breadths at both the phylum (5% (PS) to 49.91% (PS & PFOA)) and genus levels (8% (PS) to 63.96% (PS & PFOA)). Functionally, MPs and PFASs decreased the anaerobic capacity and ammonia nitrogen utilization of rhizosphere bacteria. This study enhances our understanding of the microecological responses of macrophyte-associated bacteria to combined MP and PFAS contamination and offers insights into ecological restoration strategies and mitigating associated environmental risks.

Cation-Doped Nanocarbons for Enhanced Perfluoroalkyl Substance Removal: Exotic Bottom-Up Solution Plasma Synthesis and Characterization.

Perfluorinated alkyl substances (PFAS), such as perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), are pervasive organic contaminants that are widespread in aquatic environments, posing significant health risks to humans and wildlife. Due to their persistent nature, urgent removal is necessary. Conventional adsorbents are inefficient at removing PFOS and PFOA, highlighting the need for alternative materials. Herein, we present a synthetic method for quaternary ammonium cation-doped carbon nanoparticles (QACNs) using a solution plasma process for the efficient removal of PFOS and PFOA. QACN is formed simultaneously through a one-step discharge of nonequilibrium plasma at the interface of benzene and pyridinium chloride. The resulting material exhibited a high surface electrical charge and enhanced hydrophilicity as well as an amorphous structure of a nonporous nature, involving nanoparticles with an undefined shape. The obtained adsorbent demonstrated high adsorption efficiency and stability, adsorbing 998.45 and 889.37 mg g-1 of PFOS and PFOA, respectively, exceeding the efficiencies of conventional carbon-based adsorbents (80.89-313.15 mg g-1). The adsorption performance was dependent on the adsorbent dosage, pH of the solution, and the coexisting ionic species. Adsorption studies, including adsorption kinetics, isotherms, and thermodynamics, revealed that PFOS and PFOA were chemisorbed to the QACN surface, forming multilayers endothermically and spontaneously. Experimental and computational analyses revealed that adsorption primarily occurs via electronic interactions between the PFAS active sites and the quaternary ammonium group in the carbon framework. The slightly lower adsorption potential of the PFOS and PFOA fluorocarbon chains on the adsorbent was elucidated. Furthermore, the dispersibility of the adsorbent in solution significantly affected the adsorption performance. These findings highlight the potential of the novel synthetic method proposed in this study, offering a pathway for the development of highly effective carbon adsorbents for environmental remediation.

Breast Cancer-Related Chemical Exposures in Firefighters.

To fill a research gap on firefighter exposures and breast cancer risk, and guide exposure reduction, we aimed to identify firefighter occupational exposures linked to breast cancer. We conducted a systematic search and review to identify firefighter chemical exposures and then identified the subset that was associated with breast cancer. To do this, we compared the firefighter exposures with chemicals that have been shown to increase breast cancer risk in epidemiological studies or increase mammary gland tumors in experimental toxicology studies. For each exposure, we assigned a strength of evidence for the association with firefighter occupation and for the association with breast cancer risk. We identified twelve chemicals or chemical groups that were both linked to breast cancer and were firefighter occupational exposures, including polycyclic aromatic hydrocarbons, volatile aromatics, per- and polyfluoroalkyl substances, persistent organohalogens, and halogenated organophosphate flame retardants. Many of these were found at elevated levels in firefighting environments and were statistically significantly higher in firefighters after firefighting or when compared to the general population. Common exposure sources included combustion byproducts, diesel fuel and exhaust, firefighting foams, and flame retardants. Our findings highlight breast-cancer-related chemical exposures in the firefighting profession to guide equitable worker's compensation policies and exposure reduction.

Integrating redox-electrodialysis and electrosorption for the removal of ultra-short- to long-chain PFAS

A major challenge in per- and polyfluoroalkyl substances (PFAS) remediation has been their structural and chemical diversity, ranging from ultra-short to long-chain compounds, which amplifies the operational complexity of water treatment and purification. Here, we present an electrochemical strategy to remove PFAS from ultra-short to long-chain PFAS within a single process. A redox-polymer electrodialysis (redox-polymer ED) system leverages a water-soluble redox polymer with inexpensive nanofiltration membranes, facilitating the treatment of varied chain lengths of PFAS without membrane fouling. Our approach combines both ion migration by electrodialysis (for PFAS with chain lengths ≤C4) and electrosorption strategies (for PFAS with chain lengths ≥C6) to eliminate approximately 90% of ultra-short-, short-chain, and long-chain PFAS. At the same time, we achieve continuous desalination of the source water down to potable water level. The redox-polymer ED exhibits remarkable PFAS removal in real source water scenarios, including from matrices with 10,000 times higher salt concentrations, as well as secondary effluents from wastewaters. Additionally, the removed PFAS is mineralized with a defluorination performance between 76-100% by electrochemical oxidation, highlighting the viability of integrating the separation step with a reactive degradation process.