Perfluorobutyric Acid Research Articles

Response mechanisms of submerged macrophytes and epiphytic biofilms to single and coexisting per-and poly-fluoroalkyl substances and antibiotics stress

Combined pollutants of per- and poly-fluoroalkyl substances (PFAS) and antibiotics are commonly found in aquatic environments. This study aimed to investigate the effects of PFAS (perfluorobutyric acid (PFBA) and perfluorooctanoic acid (PFOA)) and antibiotics (tetracycline (TC) and chloramphenicol (CAP)) on Vallisneria natans (V. natans) and their epiphytic biofilms. The changes in photosynthetic pigments and oxidative damage in V. natans were altered by these pollutants. For example, the total chlorophyll was increased from 4.64 to 8.10 mg/L due to the combined pollutant of PFOA and TC. When exposed to the combined pollutant of PFBA and TC, a concentration of malondialdehyde of 28.4 nmol/g was measured, which was significantly higher than that in the control group. For combined toxicity, the PFAS and antibiotics primarily exhibited antagonistic effects within V. natans. The glycine, serine, and threonine metabolism pathways were mainly affected by the combined stress of PFBA and TC. Single pollutants of TC and CAP were found to inhibit the uptake of nutrients by V. natans, while the coexisting antibiotics enhanced the inhibitory effects of PFBA and PFOA in combined pollutant treatments. The growth of microorganisms in the epiphytic biofilms was significantly promoted by PFBA and PFOA, whereas their growth was notably inhibited by CAP. The composition of biofilms could be altered by single and combined pollutants, with antibiotics being more likely than PFAS to change the microbial communities within the biofilms. When exposed to TC and CAP, the ACE indices decreased from 1171.5 to 466.4 and 703.8, respectively.

Occurrence of per- and polyfluoroalkyl substances in drinking water in China and health risk assessment based on a probabilistic approach

Per- and polyfluoroalkyl substances (PFASs) raise concerns due to their widespread distribution, persistence, and toxicity to humans. Current studies lack the use of exposure parameters for Chinese populations and probabilistic risk assessment (PRA) to assess health risks of PFASs. To provide a scientific basis for the standards of PFASs in drinking water in China, data on concentrations of nine PFASs in 649 drinking water samples were collected from China through literature review. The highest concentration of PFASs was 17.41 ± 20.06 ng/L for perfluorobutyric acid (PFBA). Higher concentrations of PFASs were found in the southeastern coastal and in Sichuan Province. The probability of exceeding the standardized limits for drinking water for PFOA and PFOS was 2.71 % and 0.91 %. PRA and deterministic risk assessment (DRA) were used to assess non-carcinogenic risks in different age groups and provinces. Health risks of PFASs from oral exposure notably exceeded dermal contact. The Hazard Quotient (HQ) for oral exposure to perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) exceeded the acceptable level with a certain probability. The non-carcinogenic risk of exposure to PFASs in drinking water was negligible for the majority of the Chinese population. The study indicates that China should increase research on limits of PFASs in drinking water to reduce the health risks.

Bioelectricity drives transformation of nitrogen and perfluorooctanoic acid in constructed wetlands: Performances and mechanisms

In this study, constructed wetland-microbial fuel cell (CW-MFC) filled with modified basalt fiber (MBF) via iron modification was utilized for treating perfluorooctanoic acid (PFOA) containing sewage. Results showed the significant promotion by bioelectricity on ammonium and total nitrogen by 7.80–8.14 %. Although such enhancement was suppressed by PFOA, higher removal was still observed with closed circuit, and PFOA removal also increased by 9.05 %. Bioelectricity contributed to enrichment of bacteria involved in nitrifying (Nitrospira and Ellin6067), denitrifying (like Thauera and Dechloromonas), iron redox (Geobacter), and sulfate-reducing (Desulfobacter), aligned with up-regulated of functional genes, including amoA, narG , napA, narK, narS, nrfA, sulp and sqr. Enrichment of autohydrogenotrophic and sulfide-oxidizing autotrophic denitrifiers, and nitrate dependent iron oxidation bacteria by bioelectricity all promoted denitrification. Moreover, bioelectricity boosted relative abundance of organic compounds degradation enzymes, such as dehydrogenase, decarboxylase, and dehalogenase, supporting the enhancement on PFOA removal. Generally, PFOA was converted to short-chain perfluorocarboxylic acids (PFCAs) via decarboxylation, hydroxylation, HF elimination, hydrolysis, F- elimination, C-C bond scission, and dehydration in CW-MFC. The final PFCAs-products determined was perfluorobutyric acid. This work estimated feasibility of treating PFOA containing sewage by CM-MFC, and offered new insights on enhancing mechanisms of nitrogen and PFOA conversion.

Screening of Characteristic Pollutants and Risk Pollutants in Different Media in the Yangtze River Basin Using Comprehensive Evaluation and Risk Quotient Methods

A variety of pollutants have frequently been detected in the Yangtze River Basin with the rapid economic development, the population increase, and the acceleration of urbanization, which threaten the aquatic ecosystem and human health. A multi-criteria comprehensive evaluation method was developed to identify the characteristic pollutants, and the risk quotient method was used to derive the risk pollutants in water and sediment samples in this article. A total of 155 pollutants from 11 categories were detected in the Yangtze River Basin according to the literature research. Then, the K-means method was used to analyze the cluster of pollutant comprehensive scores. All pollutants were graded based on their scores and recorded as Ⅰ-Ⅵ according to the number of cases in each cluster. A total of 43 pollutants with high scores of Ⅰ and Ⅱ were listed as the characteristic pollutants, which included 11 polycyclic aromatic hydrocarbons, 11 organochlorine pesticides, 10 polychlorinated biphenyls, eight dioxins, two heavy metals, and one phthalate ester. The top five median concentrations of contaminants in water and sediment samples were heavy metals, polycyclic aromatic hydrocarbons, phthalates esters, bisphenols, and pharmaceuticals and personal care products. According to the principle of risk maximization, the risk entropy value （RQ） was calculated based on the highest pollutant concentration. A total of 38 risky pollutants were screened in the water samples （RQ ≥ 0.1）. There were eight high-risk pollutants with RQ ≥ 1, which included benzo[a,h]-anthracene, anthracene, benzo[a]anthracene, pyrene, methoxychlor, aldrin, 2,4'-dichlorodiphenyl, and cadmium. There were 15 high-risk contaminants in the sediment, which included benzo[b]fluoranthene, anthracene, acenaphthene, fluoranthene, cadmium, lead, chromium, arsenic, selenium, dibutyl phthalate, dimethyl phthalate, diisobutyl phthalate, norfloxacin, perfluorobutyric acid, and bisphenol A. The risk pollutants contained emerging pollutants, which included ten pollutants in water samples and nine pollutants in sediments. Antibiotic pollutants accounted for the largest proportion of these emerging pollutants. The information provided in this article may be useful for the relevant departments to monitor the pollutants and propose management programs for the Yangtze River Basin. Additionally, it is of great significance for the ecological environmental protection and management of the Yangtze River Basin.

Microfiltration Membrane Pore Functionalization with Primary and Quaternary Amines for PFAS Remediation: Capture, Regeneration, and Reuse.

The widespread production and use of multi-fluorinated carbon-based substances for a variety of purposes has contributed to the contamination of the global water supply in recent decades. Conventional wastewater treatment can reduce contaminants to acceptable levels, but the concentrated retentate stream is still a burden to the environment. A selective anion-exchange membrane capable of capture and controlled release could further concentrate necessary contaminants, making their eventual degradation or long-term storage easier. To this end, commercial microfiltration membranes were modified using pore functionalization to incorporate an anion-exchange moiety within the membrane matrix. This functionalization was performed with primary and quaternary amine-containing polymer networks ranging from weak to strong basic residues. Membrane loading ranged from 0.22 to 0.85 mmol/g membrane and 0.97 to 3.4 mmol/g membrane for quaternary and primary functionalization, respectively. Modified membranes exhibited a range of water permeances within approximately 45-131 LMH/bar. The removal of PFASs from aqueous streams was analyzed for both "long-chain" and "short-chain" analytes, perfluorooctanoic acid and perfluorobutyric acid, respectively. Synthesized membranes demonstrated as high as 90% rejection of perfluorooctanoic acid and 50-80% rejection of perfluorobutyric acid after 30% permeate recovery. Regenerated membranes maintained the capture performance for three cycles of continuous operation. The efficiency of capture and reuse can be improved through the consideration of charge density, water flux, and influent contaminant concentration. This process is not limited by the substrate and, thus, is able to be implemented on other platforms. This research advances a versatile membrane platform for environmentally relevant applications that seek to help increase the global availability of safe drinking water.

Efficient defluorination of PFOA by vacuum ultraviolet coupling with sulfite and iodide

Perfluorooctanoic acid (PFOA), as an anthropogenic persistent contaminant, is widely distributed in the natural aquatic environment and has been a considerable threat to ecological security and human health. In this work, we propose and evaluate the vacuum ultraviolet (VUV)/sulfite-iodide system under N2 saturated condition for the decomposition of PFOA. The in situ generated hydrated electrons (eaq−) were demonstrated to be the main active species responsible for the PFOA degradation. With observation of the intermediate products, two major degradation pathways of PFOA in VUV/sulfite-iodide system were proposed: H/F exchange and chains shortening. A significant enhancement of PFOA defluorination was observed with increasing pH values from 9.0 to 12.0, which can be explained by the decreasing quenching effect of eaq− and accelerated disproportionation of I2 to I− and IO3−. Meanwhile, VUV/sulfite-iodide system also exhibited satisfactory performance in degrading high concentration of PFOA (200 μM). However, the presence of Cl−, NO3−, and humic acid inhibited the removal of PFOA via various reaction mechanism. The VUV/sulfite-iodide system was effective toward the chosen PFCAs (trifluoroacetic acid (TFA) and perfluorobutyric acid (PFBA)), demonstrating a chain length independence on the degradation of PFCAs, supporting its broad applicability.

Generic method for the detection of short & long chain PFAS extended to the lowest concentration levels of SERS capability

The detection of the highly toxic per- and polyfluoroalkyl substances, PFAS, constitutes a challenging task in terms of developing a generic method that could be rapid and applicable simultaneously to both long and short-chain PFAS at ppt concentration level. In the present study, the method introduced by the USA Environmental Protection Agency, EPA, to detect surfactants, using methylene blue, MB, which is identified an ideal candidate for PFAS-MB ion pairing, is extended at the lowest concentration range by a simple additional step that involves the dissociation of the ion pairs in water. In this work, Surface Enhanced Raman Scattering, SERS, is applied via Ag nanocolloidal suspensions to probe MB and indirectly either/or both short-chain (perfluorobutyric acid, PFBA) and long-chain (perfluoloctanoic acid, PFOA) PFAS downt to 5 ppt. This method, which can be further optimized to sub-ppt level via a custom-made SERS-PFAS dedicated Raman system, offers the possibility to be applied to either specific PFAS (both short and long-chain) in a targeted analysis or to total PFAS in a non-targeted analysis at very low detection limits, following any type of MB detection method in aqueous solutions and obviously with any type of SERS substrate.

Regulation and synthesis of metal–organic frameworks through mixed-ligand strategy: A pathway to enhance adsorption of perfluoroalkyl acids

Metal-organic frameworks (MOFs) have been regarded as extremely promising adsorbent materials, with the repetitive coordination assembly of inorganic metal ions and organic ligands constituting their reticular structure and abundant pores. Herein, a ligand mixing approach to synthesizing and regulating MOFs is provided. By mixing multiple solvents and adding modifiers, imidazole-based linkers can be prepared MOFs with mixed ligand components at room temperature. In this study, we prepared four mixed-ligand MOFs: Zn(aIM + bIM), Zn(mIM + bIM), Zn(aIM + mIM), and Zn(mIM + 2-mbIM). Series of characterizations by SEM, XRD, NMR, etc. confirmed the successful preparation of mixed-ligand MOFs, and they exhibited the different surface areas, pore sizes, and surface properties. And the adsorption capabilities for perfluoroalkyl acids (PFAAs) were compared among the prepared MOFs adsorbents. Among them, Zn(aIM + bIM) consisting of benzimidazole and imidazole-2-formaldehyde linker possessed the optimum adsorption performance, with an equilibrium adsorption capacity qe of 245 mg/g for perfluorobutyric acid, and the calculated maximum adsorption capacity qm of 439 mg/g. And for the other chain lengths of perfluoroalkyl acids, the adsorption results are also acceptable. The potential adsorption mechanism and the reasons for the performance enhancement are discussed based on relevant characterization and simulation. It was proved that the ligand mixing strategy can provide new insights into the development of high-performance MOFs adsorbents for addressing environmental concerns.

TPU/PEI nanofibers for the efficient removal of PFOA and its analogs: Effect of pH, humic acid and co-existing ions, mechanism, and regenerative effects

Perfluorooctanoic acid (PFOA) and its analogs, such as perfluorocaproic acid (PFHxA), perfluorobutyric acid (PFBA), and perfluoro(2-methyl-3-oxahexanoic) acid (GenX), present environmental contamination concerns due to their toxicity. To addressing this, in this study, we have explored the utility of thermoplastic polyurethane/polyethyleneimine (TPU/PEI) nanofibers, synthesized via electrospinning, for the efficient removal of PFOA and its analogs from aqueous solutions. Combining the positively charged amino groups of PEI and hydrophobicity of TPU potentially enhances adsorption. Further, the TPU/PEI nanofibers exhibit a distinctive nano-phase separation morphology, creating abundant adsorption sites conducive to PFAS binding. Batch adsorption experiments indicated that TPU/PEI nanofibers possess notable adsorption capacities for PFOA and its analogs. The observed adsorption capacities were ranked as follows: PFOA (0.931 mmol/g) > PFHxA (0.872 mmol/g) > PFBA (0.827 mmol/g) > GenX (0.771 mmol/g), thus showing a correlation with their respective octanol–water partition coefficient (Kow) values. Both inorganic ions and organic matter exerted more pronounced adverse effects on the adsorption of PFBA and GenX than on those of PFOA and PFHxA. This observation can be linked to competitive adsorption with PFAS. Impressively, the TPU/PEI nanofibers maintained a high removal efficiency across multiple regeneration cycles, with more than 95 % adsorption capacity retained after five cycles. To the best of our knowledge, this study is the inaugural demonstration of utilizing a TPU and PEI blend for remediation of both long-chain and short-chain PFAS in highly polluted wastewater, positioning it as a promising, accessible material for such applications.

Laponite-activated AIE supramolecular assembly with modulating multicolor luminescence for logic digital encryption and perfluorinated pollutant detection

Recently, the non-covalently activated supramolecular scaffold method has become a prominent research area in the field of intelligent materials. Here, the inorganic clay (LP) promoted the AIE properties of 4,4′,4″,4‴-(ethene-1,1,2,2-tetrayltetrakis(benzene-4,1-diyl))tetrakis(1-ethylpyridin-1-ium) (P-TPE), showing an astonishing 42-fold enhancement of the emission intensity of the yellow-green luminescence and a 34-fold increase of the quantum yield via organic-inorganic supramolecular strategy as well as the efficient light-harvesting properties (energy transfer efficiency up to 33 %) after doping with the dye receptor Rhodamine B. Furthermore, the full-color spectral regulation, including white light, was achieved by adjusting the ratio of the donor to the acceptor component and co-assembling with the carbon dots (CD). Interestingly, this TPE-based non-covalently activated full-color supramolecular light-harvesting system (LHS) could be achieved not only in aqueous media but also in the hydrogel and the solid state. More importantly, this panchromatic tunable supramolecular LHS exhibited the multi-mode and quadruple digital logic encryption property as well as the specific detection ability towards the perfluorobutyric acid and the perfluorobutanesulfonic acid, which are harmful to human health in drinking water. This result develops a simple, convenient and effective approach for the intelligent anti-counterfeiting and the pollutant sensing.

Assessment and Comparison of Early Developmental Toxicity of Six Per- and Polyfluoroalkyl Substances with Human Embryonic Stem Cell Models.

Per- and polyfluoroalkyl substances (PFAS) are extensively utilized in varieties of products and tend to accumulate in the human body including umbilical cord blood and embryos/fetuses. In this study, we conducted an assessment and comparison of the potential early developmental toxicity of perfluorooctanoic acid (PFOA), undecafluorohexanoic acid (PFHxA), heptafluorobutyric acid, perfluorooctanesulfonate (PFOS), perfluorohexanesulfonate, and perfluorobutyric acid at noncytotoxic concentrations relevant to human exposure using models based on human embryonic stem cells in both three-dimensional embryoid body (EB) and monolayer differentiation configurations. All six compounds influenced the determination of cell fate by disrupting the expression of associated markers in both models and, in some instances, even led to alterations in the formation of cystic EBs. The expression of cilia-related gene IFT122 was significantly inhibited. Additionally, PFOS and PFOA inhibited ciliogenesis, while PFOA specifically reduced the cilia length. Transcriptome analysis revealed that PFOS altered 1054 genes and disrupted crucial signaling pathways such as WNT and TGF-β, which play integral roles in cilia transduction and are critical for early embryonic development. These results provide precise and comprehensive insights into the potential adverse health effects of these six PFAS compounds directly concerning early human embryonic development.

Occurrence and Risk Assessment of Perfluoroalkyl Substances in Surface Water of Hefei City, Southeast China

In this work, the spatial distribution, potential sources, and risk assessment of perfluoroalkyl substances (PFASs) were investigated at 22 surface water sampling sites in Hefei City. The study encompassed 11 distinct types of PFASs, which included 7 perfluoroalkyl carboxylic acids (PFCAs) and 4 perfluoroalkyl sulfonic acids (PFSAs). The findings indicated that the overall concentration of PFASs varied between 12.96 to 545.50 ng/L, with perfluorooctanoic acid (PFOA), perfluorobutanesulfonic acid (PFBS), perfluorobutyric acid (PFBA), and perfluorohexanoic acid (PFHxA) being the most prevalent, contributing to an average of 71% of the total PFASs concentration. Principal component analysis (PCA) elucidated the primary sources of PFASs, which included industrial emissions, fluoropolymer production and treatment, textile processing, and the impact of the electroplating industry. Employing the risk quotient (RQ) method facilitated the assessment of ecological risks associated with PFASs in surface water within the study area, suggesting that the current concentrations of PFASs in Hefei’s surface water pose a relatively low ecological risk. However, the long-term ecological effects of PFASs cannot be overlooked due to their potential for long-range transport and the cumulative nature of biological food chains.

Per- and polyfluoroalkyl substances in waterbird feathers around Poyang Lake, China: Compound and species-specific bioaccumulation

As a nondestructive means of environmental monitoring, bird feathers have been used to analyze levels of per- and polyfluoroalkyl substances (PFASs) in specific environments. In this study, feather samples from 10 waterbird species around Poyang Lake were collected, and a pretreatment method for PFASs in feathers was optimized. The results showed that a combined cleaning method using ultrapure water and n-hexane effectively removed external PFASs. Twenty-three legacy and emerging PFASs were identified in the feathers of waterbirds, of which hexafluoropropylene oxides (HFPOs), chlorinated polyfluoroalkyl ether sulfonates (Cl-PFESAs), and sodium p-perfluorinated noneoxybenzene sulfonate (OBS) were reported for the first time, with their concentrations ranging from 0.060–2.4 ng·g−1 dw, 0.046–30 ng·g−1 dw, and lower than the method detection limit to 30 ng·g−1 dw, respectively. Compound- and species-specific bioaccumulation of PFASs was observed in the feathers of different waterbird species, suggesting that different PFAS types can be monitored through the selection of different species. Moreover, the concentrations of most PFCAs (except perfluorobutyric acid), perfluorooctane sulfonate (PFOS), and perfluorooctane sulfonamide (FOSA) were significantly positively correlated with δ15N (p < 0.05), while the concentrations of HFPOs, Cl-PFESAs, and OBS had significant positive correlations with δ13C. This indicates that the bioaccumulation of legacy and emerging PFASs in waterbird feathers is affected by their trophic level, feeding habits, and foraging area.

Operating performance of sequential batch system with calcium-modified basalt fiber bio-nest exposed to two typical perfluoroalkyl compounds (PFOA and PFBA)

The effects of per- and polyfluoroalkyl substances (PFASs) on the application of sequential batch system with basalt fiber as a biological carrier material have been rarely reported. This study explored the decontamination performance, extracellular polymeric substances (EPS) and microbial community structure of sequencing batch system with calcium-modified basalt fiber (Ca-MBF) bio-nest exposed to perfluorooctanoic acid (PFOA) and perfluorobutyric acid (PFBA). The results showed that 0.5 mg/L PFOA and PFBA both inhibited nitrification by 24.67 % and 19.47 %, while promoted denitrification by 16.54 % and 11.15 %, respectively. Overall, compared to PFBA, PFOA inhibited the removal of total nitrogen (TN) and total phosphorus (TP) by 11.27 % and 9.49 %, respectively. Further analysis of EPS showed that under PFOA exposure, the total EPS and polysaccharide (PS) content decreased by 34.57 % and 40.78 %, respectively. In addition, PFOA and PFBA exhibited a phenomenon of initially promoting by 89.21 % and 55.29 %, and subsequently inhibiting on protein (PN) content by 50.22 % and 51.37 %, respectively. Analyses of Illumina Miseq sequencing showed that PFOA and PFBA exposure for 50 days both inhibited the richness and diversity of microbial communities, and the inhibitory effect of PFOA was greater than that of PFBA. In addition, PFOA and PFBA respectively domesticated the resistant bacteria Meganema and Acinetobacter. These results may provide valuable information for ecological restoration and biodegradation of PFOA and PFBA.

Understanding the effects of per- and polyfluoroalkyl substances on early skin development: Role of ciliogenesis inhibition and altered microtubule dynamics

Per- and polyfluoroalkyl substances (PFAS) are a class of highly stable chemicals, widely used in everyday products, and widespread in the environment, even in pregnant women. While epidemiological studies have linked prenatal exposure to PFAS with atopic dermatitis in children, little is known about their toxic effects on skin development, especially during the embryonic stage. In this study, we utilized human embryonic stem cells to generate non-neural ectoderm (NNE) cells and exposed them to six PFAS (perfluorooctanoic acid (PFOA), undecafluorohexanoic acid (PFHxA), heptafluorobutyric acid (PFBA), perfluorooctane sulfonate (PFOS), perfluorohexane sulfonate (PFHxS) and perfluorobutyric acid (PFBS)) during the differentiation process to assess their toxicity to early skin development. Our results showed that PFOS altered the spindle-like morphology of NNE cells to a pebble-like morphology, and disrupted several NNE markers, including KRT16, SMYD1, and WISP1. The six PFAS had a high potential to cause hypohidrotic ectodermal dysplasia (HED) by disrupting the expression levels of HED-relevant genes. Transcriptomic analysis revealed that PFOS treatment produced the highest number (1156) of differentially expressed genes (DEGs) among the six PFAS, including the keratinocyte-related genes KRT6A, KRT17, KRT18, KRT24, KRT40, and KRT81. Additionally, we found that PFOS treatment disturbed several signaling pathways that are involved in regulating skin cell fate decisions and differentiation, including TGF-β, NOTCH, Hedgehog, and Hippo signaling pathways. Interestingly, we discovered that PFOS inhibited, by partially interfering with the expression of cytoskeleton-related genes, the ciliogenesis of NNE cells, which is crucial for the intercellular transduction of the above-mentioned signaling pathways. Overall, our study suggests that PFAS can inhibit ciliogenesis and hamper the transduction of important signaling pathways, leading potential congenital skin diseases. It sheds light on the underlying mechanisms of early embryonic skin developmental toxicity and provides an explanation for the epidemiological data on PFAS. Environmental implicationWe employed a model based on human embryonic stem cells to demonstrate that PFOS has the potential to elevate the risk of hypohidrotic ectodermal dysplasia. This is achieved by targeting cilia, inhibiting ciliogenesis, and subsequently disrupting crucial signaling pathways like TGF-β, NOTCH, Hedgehog, and Hippo, during the early phases of embryonic skin development. Our study highlights the dangers and potential impacts of six PFAS pollutants on human skin development. Additionally, we emphasize the importance of closely considering PFHxA, PFBA, PFHxS, and PFBS, as they have shown the capacity to modify gene expression levels, albeit to a lesser degree.

Legacy and alternative per-and polyfluoroalkyl substances (PFASs) in the Bohai Bay Rim: Occurrence, partitioning behavior, risk assessment, and emission scenario analysis

The use of alternative per- and polyfluoroalkyl substances (PFASs) has been practiced because of the restrictions on legacy PFASs. However, knowledge gaps exist on the ecological risks of alternatives and relationships between restrictions and emissions. This study systematically analyzed the occurrence characteristics, water-sediment partitioning behaviors, ecological risks, and emissions of legacy and alternative PFASs in the Bohai Bay Rim (BBR). The mean concentration of total PFASs was 46.105 ng/L in surface water and 6.125 ng/g dry weight (dw) in sediments. As an alternative for perfluorooctanoic acid (PFOA), hexafluoropropylene oxide dimer acid (GenX) had a concentration second only to PFOA in surface water. In sediments, perfluorobutyric acid (PFBA) and GenX were the two predominant contaminants. In the water-sediment partitioning system, GenX, 9-chlorohexadecafluoro-3-oxanone-1-sulfonic acid (F-53B), and 11-chloroeicosafluoro-3-oxaundecane-1-sulfonic acid (8:2 Cl-PFESA) tended to be enriched towards sediments. The species sensitivity distribution (SSD) models revealed the low ecological risks of PFASs and their alternatives in the BBR. Moreover, predicted no-effected concentrations (PNECs) indicated that short-chain alternatives like PFBA and perfluorobutane sulfonate (PFBS) were safer for aquatic ecosystems, while caution should be exercised when using GenX and F-53B. Due to the incremental replacement of PFOA by GenX, cumulative emissions of 1317.96 kg PFOA and 667.22 kg GenX were estimated during 2004–2022, in which PFOA emissions were reduced by 59.2 % due to restrictions implemented since 2016. If more stringent restrictions are implemented from 2023 to 2030, PFOA emissions will further decrease by 85.0 %, but GenX emissions will increase by an additional 21.3 %. Simultaneously, GenX concentrations in surface water are forecasted to surge by 2.02 to 2.45 times in 2023. This study deepens the understanding of PFAS alternatives and assists authorities in developing policies to administer PFAS alternatives.

Porous Fe-doped graphitized biochar: An innovative approach for co-removing per-/polyfluoroalkyl substances with different chain lengths from natural waters and wastewater

Legacy long-chain per-/polyfluoroalkyl substances (PFAS) are being replaced by short-chain homologs, which have been widely detected in the environment. To achieve the co-removal of different chain length PFAS, this study systematically explored the single and synergistic effects of FeCl3-impregnation, wet ball-milling and different carbonization temperatures on the surface chemistry and pore structures of different biochars as well as sorption performances and mechanisms towards long-chain perfluorooctanoic acid (PFOA) and short-chain perfluorobutyric acid (PFBA). As a consequence, we presented a new method to synthesize magnetic sorbents by wet ball-milling with FeCl3 solution and high-temperature carbonization. Through this process, we tailored a magnetic porous Fe-doped graphitized biochar (named Fe-M−BC900) that contains abundant dispersed positive iron sites with stable Fe0/Fe3C, multi-stage pore structure, highly hydrophobic graphite-like carbon, and O-containing functional groups. Fe-M−BC900 exhibited a high sorption capacity of 10.1 mg PFBA/g and 39.1 mg PFOA/g. PFAS sorption on Fe-M−BC900 was mainly governed by pore-filling, electrostatic interaction, and hydrophobic partitioning. The sorption of PFBA on Fe-doped biochars depends more on electrostatic interaction and is less affected by hydrophobic partitioning compared to PFOA. Finally, we demonstrated that Fe-M−BC900 performed high co-removal rates (>96 %) for a wide range of legacy and emerging PFAS with different chain lengths and functional groups in natural waters (∑PFAS: 142 ∼ 265 μg/L) and simulated wastewater (∑PFAS: 600 μg/L), with a high relative sorption capacity of > 91 %, even after four consecutive recycling processes. This new adsorbent could help water facilities comply with upcoming PFAS regulations if tested on a larger scale.

Binding interaction of environmental DNA with typical emerging perfluoroalkyl acids and its impact on bioavailability

As the replacement compounds of perfluoroalkyl acids (PFAAs), emerging PFAAs generally exhibit equal or more hazardous toxicity than legacy PFAAs. Numerous DNA as environmental organic matters coexists with emerging PFAAs, but their interactions and the resulting interaction impacts on the bioavailability of emerging PFAAs remain insufficiently understood. Here, we studied the binding strength and mechanism between DNA and emerging PFAAs (perfluorobutyric acid, perfluorobutylsulfonic acid, and hexafluoropropylene oxide dimer acid) using perfluorooctanoic acid as the control, and further investigated the impacts of DNA binding on the bioavailability of the emerging PFAAs. Isothermal titration calorimetry and quantum chemical calculation found that the emerging PFAAs could bind with DNA bases (main thymine) by van der Waals force and halogen-bond, showing the binding affinities in the range of 7.87 × 104 to L/mol to 6.54 × 106 L/mol. The PFAAs-DNA binding significantly decreased the bioavailability of the PFAAs in both seedlings and plants of pakchoi (Brassica chinensis L.), with little differences in bioavailability change extent among PFAAs. The findings highlight the universality and similarity of the DNA binding effects on PFAAs bioavailability, which can be the natural detoxification mechanism for response to the PFAAs pollution.

Spherical amino-functionalized covalent organic frameworks: Synthesis and adsorption performance toward perfluorinated compounds

Perfluorinated compounds (PFCs) are widely used in textiles, fire protection, metal electroplating, and semiconductor production owing to their hydrophobic and oil-repellent characteristics. However, they are also persistent organic pollutants. The uncontrolled discharge of PFCs into the environment has led to serious global pollution. PFCs pose severe reproductive, neural, immune, and other threats to human health by accumulating through the food chain. Thus, the development and application of high-performance extraction materials has become a research hotspot in efforts to achieve the accurate detection of trace PFCs in environmental waters. Most traditional PFC adsorbents present a number of disadvantages, such as low adsorption selectivity, slow diffusion, and poor reusability. Covalent organic frameworks (COFs) are crystalline polymers with ordered porous structures, large specific surface areas, and high chemical and thermal stability. These frameworks can easily be functionalized for the desired purpose. In this paper, spherical amino-functionalized COFs (denoted COF-NH2) were fabricated via a two-step method to effectively enrich/remove PFCs from water. First, vinyl covalent organic framework (Vinyl COF) was synthesized at room temperature using 1,4-diradical-2,5-divinylbenzene (Dva) and 1,3,5-tris(4-aminophenyl)benzene (Tab) as building blocks. Then, thioether-bridged aromatic amine-functionalized spherical COF-NH2 was synthesized through a thiol-alkenyl click reaction using 4-aminothiophenol as the functional monomer. COF-NH2 showed good dispersion in water owing to its abundant amino groups, forming multiple hydrogen bonds with the F atoms of PFCs. The synergistic hydrophobic interactions between the organic skeleton of the COF and alkyl carbon chains of the PFCs led to enhanced adsorption efficiency. The produced Vinyl COF and COF-NH2 were characterized by Fourier transform infrared spectroscopy (FT-IR), field-emission scanning electron microscopy (SEM), powder X-ray diffraction (PXRD), thermogravimetric analysis (TGA), and Brunner-Emmet-Teller (BET) measurements. The results confirmed that spherical COF-NH2 materials with a homogeneous size distribution were successfully fabricated. The obtained COF-NH2 microspheres had a diameter of approximately 500 nm and exhibited high thermal stability as well as a large specific surface area and pore volume. The adsorption kinetics, isotherm adsorption models, pH effects, and regeneration properties of COF-NH2 were also investigated, and the results indicated that the adsorption of PFCs by COF-NH2 conformed to the pseudo-second-order kinetic and Langmuir isotherm adsorption models. The obtained COF-NH2 microspheres can be applied over a wide pH range, and the best adsorption effect was achieved in neutral and alkaline environments. After five cycles of regeneration and reuse, the COF-NH2 microspheres retained their good adsorption efficiency for PFCs. The adsorption mechanism was mainly attributed to the synergistic effect of hydrogen bonding and hydrophobic interactions between COF-NH2 and the PFCs. The extraction efficiencies of the microspheres toward five PFCs (perfluorobutyric acid, perfluorovaleric acid, perfluorohexanoic acid, perfluorooctanoic acid, and perfluorononanoic acid) in tap and Pearl River water samples were between 91.76% and 98.59%, with relative standard deviations (RSDs) (n=3) varying from 0.82% to 3.8%; these findings indicate that the obtained COF-NH2 is promising for the extraction of PFCs from complex water samples. Given their uniform size distribution, high thermal stability, good adsorption performance, and reusability, the novel spherical COF-NH2 materials developed in this study may be used as solid-phase extraction materials or filled into liquid chromatographic columns for the enrichment, separation, and detection of PFCs in complex samples.

Thermal Decomposition of Two Gaseous Perfluorocarboxylic Acids: Products and Mechanisms.

The thermal decomposition products and mechanisms of per- and polyfluoroalkyl substances (PFASs) are poorly understood despite the use of thermal treatment to remediate PFAS-contaminated media. To identify the thermal decomposition products and mechanisms of perfluorocarboxylic acids (PFCAs), gaseous perfluoropropionic acid (PFPrA) and perfluorobutyric acid (PFBA) were decomposed in nitrogen and oxygen at temperatures from 200 to 780 °C. In nitrogen (i.e., pyrolysis), the primary products of PFPrA were CF2═CF2, CF3CF2H, and CF3COF. CF3CF═CF2 was the dominant product of PFBA. These products are produced by HF elimination (detected as low as 200 °C). CF4 and C2F6 were observed from both PFCAs, suggesting formation of perfluorocarbon radical intermediates. Pyrolysis products were highly thermally stable, resulting in poor defluorination. In oxygen (i.e., combustion), the primary product of both PFPrA and PFBA below 400 °C was COF2, but the primary product was SiF4 above 600 °C due to reactions with the quartz reactor. Oxygen facilitated thermal defluorination by reacting with PFCAs and with pyrolysis products (i.e., fluoroolefins and fluorocarbon radicals). Platinum improved combustion of PFCAs to COF2 at temperatures as low as 200 °C, while quartz promoted the combustion of PFCAs into SiF4 at higher temperatures (>600 °C), highlighting the importance of surface reactions that are not typically incorporated into computational approaches.