Heptafluorobutyric Acid Research Articles

Analysis of Aminoglycoside Antibiotics: A Challenge in Food Control.

Aminoglycosides are a widely used group of antibiotics in veterinary medicine. However, misuse and abuse of these drugs can lead to residues in the edible tissues of animals. Due to the toxicity of aminoglycosides and the exposure of consumers to the emergence of drug resistance, new methods are being sought to determine aminoglycosides in food. The method presented in this manuscript describes the determination of twelve aminoglycosides (streptomycin, dihydrostreptomycin, spectinomycin, neomycin, gentamicin, hygromycin, paromomycin, kanamycin, tobramycin, amikacin, apramycin, and sisomycin) in thirteen matrices (muscle, kidney, liver, fat, sausages, shrimps, fish honey, milk, eggs, whey powder, sour cream, and curd). Aminoglycosides were isolated from samples with extraction buffer (10 mM NH4OOCH3, 0.4 mM Na2EDTA, 1% NaCl, 2% TCA). For the clean-up purpose, HLB cartridges were used. Analysis was performed using ultra-high-performance liquid chromatography coupled with tandem mass spectrometry (UHPLC-MS/MS) with a Poroshell analytical column and a mobile phase of acetonitrile and heptafluorobutyric acid. The method was validated according to Commission Regulation (EU) 2021/808 requirements. Good performance characteristics were obtained for recovery, linearity, precision, specificity, and decision limits (CCα). This simple and high-sensitivity method can determine multi-aminoglycosides in various food samples for confirmatory analysis.

Bioaccumulation and risk mitigation of legacy and novel perfluoroalkyl substances in seafood: Insights from trophic transfer and cooking method

Per- and polyfluoroalkyl substances (PFAS) have widespread application in industrial and civil areas due to their unique physical and chemical properties. With the increasingly stringent regulations of legacy PFAS, various novel alternatives have been developed and applied to meet the market demand. Legacy and novel PFAS pose potential threats to the ecological safety of coastal areas, however, little is known about their accumulation and transfer mechanism, especially after cooking treatment. This study investigated the biomagnification and trophic transfer characteristics of PFAS in seafood from the South China Sea, and assessed their health risks after cooking. Fifteen target PFAS were all detected in the samples, of which perfluorobutanoic acid (PFBA) was dominant with concentrations ranging from 0.76 to 4.12 ng/g ww. Trophic magnification factors (TMFs) > 1 were observed for perfluorooctane sulfonate (PFOS) and 6:2 chlorinated polyfluoroalkyl ether sulfonic acid (F-53B), indicating that these compounds experienced trophic magnification in the food web. The effects of different cooking styles on PFAS occurrence were further explored and the results suggested that ΣPFAS concentrations increased in most organisms after baking, while ΣPFAS amounts decreased basically after boiling and frying. Generally, there is a low health risk of exposure to PFAS when cooked seafood is consumed. This work provided quantitative evidence that cooking methods altered PFAS in seafood. Further, suggestions to mitigate the health risks of consuming PFAS-contaminated seafood were provided.

Ion Exchange MIEX® GOLD Resin as a Promising Sorbent for the Removal of PFAS Compounds

Per- and polyfluoroalkyl substances (PFASs) are synthetic compounds, which have been widely produced, used, and recently identified as extremely toxic chemicals, and are responsible for serious environmental and human health risks. In this study, the removal efficiency of MIEX® GOLD resin was tested against six PFAS compounds including perfluorobutanoic acid (PFBA), perfluorobutanesulfonic acid (PFBS), perfluorohexanoic acid (PFHxA), perfluorohexanesulfonic acid (PFHxS), perfluorooctanoic acid (PFOA), and perfluorooctanesulfonic acid (PFOS). The removal of PFASs and the regeneration of resin (NaCl-saturated methanol) were achieved via adsorption and desorption mechanisms. In all cases, the removal efficiency was greater than 99% where the volume ratio of 1 ppm PFAS to resin was maintained at 50-bed volume. Furthermore, the adsorption capacity of MIEX® GOLD resin was studied for PFOA and PFHxS and achieved 1.05 ± 0.01 g PFOA adsorption and 1.01 ± 0.04 g PFHxS adsorption per gram of resin. In addition, a detailed study on the interference of natural organic matter (NOM) and inorganic matter was carried out against PFHxA, PFOA, and PFOS. The presence of 10 ppm NOM (5 ppm tannic acid + 5 ppm humic acid) and 25 ppm inorganic matter (5 ppm nitrate + 20 ppm sulfate) showed no noticeable interference in the removal of selected PFAS compounds. Compared to sulfonic acid-containing PFASs, the interference of organic and inorganic matter on carboxylic acid-containing PFASs was slightly higher. The regeneration of PFAS-adsorbed resin was studied using a mixed solution containing 70% methanol and saturated NaCl. Desorption of PFHxS, PFOS, and PFOA was found to be 98.3, 100, and 43.3%, respectively. The results again indicate that the resin regeneration is strongly affected by the functional group of PFASs; i.e., resin with sulfonic acid-containing PFAS is much easier to regenerate than carboxylic acid-containing PFAS compounds. All the PFAS analyses were performed by using mass spectroscopy and liquid chromatography–mass spectroscopy. In conclusion, this study confirms the remarkable efficiency of MIEX® GOLD resin in removing PFAS compounds, even in the presence of a high concentration of organic and inorganic interferences, and its capacity to be regenerated for repeated usage. These advantages make MIEX® GOLD a promising product for the remediation of PFAS-contaminated water. This study in the broader sense proves that MIEX® GOLD is a promising adsorbent and provides the ground for future study to treat contaminated groundwater.

Surface modification using heptafluorobutyric acid to produce highly stable Li metal anodes

The Li metal is an ideal anode material owing to its high theoretical specific capacity and low electrode potential. However, its high reactivity and dendritic growth in carbonate-based electrolytes limit its application. To address these issues, we propose a novel surface modification technique using heptafluorobutyric acid. In-situ spontaneous reaction between Li and the organic acid generates a lithiophilic interface of lithium heptafluorobutyrate for dendrite-free uniform Li deposition, which significantly improves the cycle stability (Li/Li symmetric cells >1200 h at 1.0 mA cm−2) and Coulombic efficiency (>99.3%) in conventional carbonate-based electrolytes. This lithiophilic interface also enables full batteries to achieve 83.2% capacity retention over 300 cycles under realistic testing condition. Lithium heptafluorobutyrate interface acts as an electrical bridge for uniform lithium-ion flux between Li anode and plating Li, which minimizes the occurrence of tortuous lithium dendrites and lowers interface impedance.

Mechanistic Investigations of Thermal Decomposition of Perfluoroalkyl Ether Carboxylic Acids and Short-Chain Perfluoroalkyl Carboxylic Acids.

In this study, we investigated the thermal decomposition mechanisms of perfluoroalkyl ether carboxylic acids (PFECAs) and short-chain perfluoroalkyl carboxylic acids (PFCAs) that have been manufactured as replacements for phased-out per- and polyfluoroalkyl substances (PFAS). C-C, C-F, C-O, O-H, and C═C bond dissociation energies were calculated at the M06-2X/Def2-TZVP level of theory. The α-C and carboxyl-C bond dissociation energy of PFECAs declines with increasing chain length and the attachment of an electron-withdrawing trifluoromethyl (-CF3) group to the α-C. Experimental and computational results show that the thermal transformation of hexafluoropropylene oxide dimer acid to trifluoroacetic acid (TFA) occurs due to the preferential cleavage of the C-O ether bond close to the carboxyl group. This pathway produces precursors of perfluoropropionic acid (PFPeA) and TFA and is supplemented by a minor pathway (CF3CF2CF2OCFCF3COOH → CF3CF2CF2· + ·OCFCF3COOH) through which perfluorobutanoic acid (PFBA) is formed. The weakest C-C bond in PFPeA and PFBA is the one connecting the α-C and the β-C. The results support (1) the C-C scission in the perfluorinated backbone as an effective PFCA thermal decomposition mechanism and (2) the thermal recombination of radicals through which intermediates are formed. Additionally, we detected a few novel thermal decomposition products of studied PFAS.

Investigation into Cationic Surfactants and Polyelectrolyte-Coated β-Zeolites for Rapid and High-Capacity Adsorption of Short- and Long-Chain PFAS

Per- and polyfluoroalkyl substances (PFASs) are aqueous contaminants associated with serious health consequences. Conventional PFAS adsorbents are limited by slow kinetics and low short-chain PFAS uptake, driving interest in high-performing alternatives. Here, β-zeolites were investigated for short- (<C8) and long-chain (≥C8) PFAS removal. β-zeolites with high (CP811C) and low (CP814E) silica/alumina ratios were coated with cetyltrimethylammonium bromide (CTAB) or poly(diallyldimethylammonium chloride) (PDADMAC) to enhance short- and long-chain PFAS retention, represented by heptafluorobutyric acid (PFBA) and perfluorooctanoic acid (PFOA). PFAS rapidly adsorbed onto β-zeolites, reaching equilibrium within 1–2 h. Greater PFOA uptake (91.87 vs 57.77 mg/g) was reported onto the silica-rich β-zeolite, CP811C. While the CTAB coatings reduced PFOA adsorption capacity by 58.7%, the PDADMAC coatings increased PFBA adsorption capacity by 51.3%. On unmodified CP811C, PFOA and PFBA exhibited maximum adsorption capacities of 181.87 and 27.89 mg/g, respectively. Fast and high-capacity adsorption make β-zeolites highly promising PFAS adsorption technology.

Losses of Ultrashort- and Short-Chain PFAS to Polypropylene Materials

Losses of long-chain poly-/per-fluoroalkyl substances (PFAS) due to adsorption on polypropylene (PP) materials have been reported in the literature. However, there is a lack of information on losses of ultrashort-/short-chain PFAS to PP materials, particularly in environmentally relevant conditions. In this study, we evaluated the losses of ultrashort-chain perfluoropropionic acid (PFPrA) and two short-chain PFAS, viz., perfluorobutanoic acid (PFBA) and perfluorobutanesulfonic acid (PFBS), to PP. Losses up to 20 ± 1% were observed for the studied PFAS after 24 h from 100 μg/L solutions. Losses varied greatly between PP tubes of different brands, probably due to differences in the availability of adsorption sites. Several processes were involved in the adsorptive losses of the three compounds. For example, charge screening and hydrophobic interactions affected the behavior of PFBS and PFBA. Lower losses observed in methanol and wastewater can be explained by the higher PFAS solubility and competition with other organics, respectively. This study highlights that laboratory-specific PFAS losses shall be carefully considered as they can prevent accurate trace analysis of short-chain PFAS. Our results will also help to improve the accuracy of future monitoring and adsorption studies of ultrashort-/short-chain PFAS.

Periodically reversing electrocoagulation technique for efficient removal of short-chain perfluoroalkyl substances from contaminated groundwater around a fluorochemical facility

Widespread distributions of short-chain perfluoroalkyl substances (PFASs) has been recognized as a crucial environmental issue. However, multiple treatment techniques were ineffective due to their high polarity and mobility, contributing to a never-ending existence in the aquatic environment ubiquitously. The present study revealed potential technique of periodically reversing electrocoagulation (PREC) to perform efficient removal of short-chain PFASs including experimental factors (in the conditions of 9 V for voltage, 600 r/min of stirring speed, 10 s of reversing period, and 2 g/L of NaCl electrolyte), orthogonal experiments, actual application, and removal mechanism. Accordingly, based upon the orthogonal experiments, the removal efficiencies of perfluorobutane sulfonate (PFBS) in simulated solution could achieve 81.0% with the optimal parameters of Fe–Fe electrode materials, addition of 665 μL H2O2 per 10 min, and pH at 3.0. The PREC was further applied for treating the actual groundwater around a fluorochemical facility, consequently the removal efficiencies for typical short-chain perfluorobutanoic acid (PFBA), perfluoropentanoic acid (PFPeA), perfluorohexanoic acid (PFHxA), PFBS, and perfluoropentane sulfonate (PFPeS) were 62.5%, 89.0%, 96.4%, 90.0%, and 97.5%, respectively. The other long-chain PFASs contaminants had superior removal with the removal efficiencies up to 97%–100%. In addition, a comprehensive removal mechanism related to electric attraction adsorption for short-chain PFASs could be verified through the morphological analysis of ultimate flocs composition. The oxidation degradation was further revealed as the other removal mechanism by suspect and nontarget screening of intermediates formed in simulated solution, as well as density functional theory (DFT) calculation theory. Moreover, the degradation pathways about one CF2O molecule or CO2 eliminated with one C atom removed in PFBS by ·OH generated from the PREC oxidation process were further proposed. As a result, the PREC would be a promising technique for the efficient removal of short-chain PFASs from severely contaminated water bodies.

Perfluoroalkyl Substances (PFAS) Affect Inflammation in Lung Cells and Tissues.

Adverse lung outcomes from exposure to per-and polyfluoroalkyl substances (PFAS) are known; however, the mechanism of action is poorly understood. To explore this, human bronchial epithelial cells were grown and exposed to varied concentrations of short-chain (perfluorobutanoic acid, perflurobutane sulfonic acid and GenX) or long-chain (PFOA and perfluorooctane sulfonic acid (PFOS)) PFAS, alone or in a mixture to identify cytotoxic concentrations. Non-cytotoxic concentrations of PFAS from this experiment were selected to assess NLRP3 inflammasome activation and priming. We found that PFOA and PFOS alone or in a mixture primed and activated the inflammasome compared with vehicle control. Atomic force microscopy showed that PFOA but not PFOS significantly altered the membrane properties of cells. RNA sequencing was performed on the lungs of mice that had consumed PFOA in drinking water for 14 weeks. Wild type (WT), PPARα knock-out (KO) and humanized PPARα (KI) were exposed to PFOA. We found that multiple inflammation- and immune-related genes were affected. Taken together, our study demonstrated that PFAS exposure could alter lung biology in a significant manner and may contribute to asthma/airway hyper-responsiveness.

Occurrence of persistent and mobile chemicals and other contaminants of emerging concern in Spanish and Portuguese wastewater treatment plants, transnational river basins and coastal water

This work investigated, during one year, the occurrence and fate of 52 contaminants of emerging concern (CECs) in transnational river basins and coastal areas of the North of Portugal and Galicia (NW Spain) and the wastewater treatment plants (WWTPs) discharging on these environments. The different CECs investigated included pharmaceuticals, personal care products, industrial chemicals, among others, of which ca. 90 % would fulfill the persistence, mobility and toxicity criteria proposed by the German Environmental Agency. The results showed the ubiquitous presence of these CECs and an incomplete removal of over 60 % of them with current conventional WWTPs. These findings highlight the requirement of a prominent and coordinated upgrade of WWTP treatments in order to meet the future European Union regulations on urban wastewater treatment and surface water quality. In fact, even some compounds exhibiting high removals, such as caffeine or xylene sulfonate, were frequently detected in river and estuarine waters at the high ng L−1 level. Thus, our preliminary risk assessment study concluded that 18 of the CECs presented a potential risk for the environment, being caffeine, sulpiride, perfluorooctanoic acid (PFOA), diclofenac, fipronil and perfluorobutanoic acid (PFBA) the most concerning ones. Yet, additional toxicity data as well as a more robust information on persistence and mobility of CECs are necessary for better estimating the magnitude of the problem and improve risk assessment. As an example, in the case of the antidiabetic metformin, recent research has revealed toxicity for model fish species at concentration levels below those found in 40 % of the river water samples analyzed in this work.

Accumulation and effects of perfluoroalkyl substances in Arabidopsis thaliana in a temperature-dependent manner: an in vitro study.

The replacement of long-chained per- and polyfluoroalkyl substances (PFAS) with their short-chained homologues may have an impact on the accumulation in plants. The extent to which PFAS are absorbed by plants may differ among species and may depend on environmental factors, including temperature. The effect of an increased temperature on root uptake and translocation of PFAS in plants has been poorly studied. In addition, very few studies have examined toxicity of environmentally realistic PFAS concentrations to plants. Here, we investigated the bioaccumulation and tissue-distribution of fifteen PFAS in Arabidopsis thaliana L. grown in vitro at two different temperatures. Additionally, we examined the combined effects of temperature and PFAS accumulation on plant growth. Short-chained PFAS mainly accumulated in the leaves. The perfluorocarboxylic acid (PFCA) concentrations in roots and leaves, and the relative contribution of PFCAs to the ΣPFAS concentrations increased with carbon chain length regardless of temperature, with the exception of perfluorobutanoic acid (PFBA). An increased uptake of PFAS in leaves and roots at higher temperatures was observed for PFAS containing either eight or nine carbon atoms and could hence potentially result in higher risks for human intake. Leaf:root ratios of PFCAs followed a U-shaped pattern with carbon chain length, which is attributed to both hydrophobicity and anion exchange. Overall, no combined effects of realistic PFAS concentrations and temperature on the growth of A. thaliana were observed. PFAS exposure positively affected early root growth rates and root hair lengths, indicating a potential effect on factors involved in root hair morphogenesis. However, this effect on root growth rate became negligible later on in the exposure, and solely a temperature effect was observed after 6 days. Temperature also affected the leaf surface area. The underlying mechanisms on how PFAS stimulates root hair growth require further examination.

Phytoremediation of perfluorochemicals: A review of its advances, feasibility and limitations

The detection of perfluorochemicals (PFCs) in various environmental compartments has raised attention and driven countermeasures to reduce their prevalence. Phytoremediation provides a feasible option for PFCs removal from the environment. Crops such as maize, carrots, lettuce, tomato and spinach have demonstrated the ability to phytoextract and phytoaccumulate PFCs. The bioconcentration factors (BCFs) of PFCs in plants widely vary with plant types, plant parts, the types of PFCs and the properties of soil. Maize straw for instance was shown to have a high BCF (35.23) for perfluorobutanoic acid in comparison to maize kernel with a BCF of only 0.229 for the same compound. Maize leaves have a BCF of 9.39 for perfluorohexane sulphonic acid and maize roots have a BCF of 8.82 for perfluorooctane sulphonic acid. Carrots were found to degrade fluorotelomers whereas silver birch and long beechfern are good accumulators of numerous PFCs. BCFs of perfluoroalkyl carboxylic acids are usually negatively correlated to the carbon chain lengths due to decreasing aqueous solubilities with increasing carbon chain lengths which impede root uptake of the compounds. PCFs phytoremediation is low cost, less energy intensive, operationally simple and environmentally friendly but has the drawbacks of inconsistent performance, long duration, and lacking evidence on mineralization of perfluoroalkyl substances. The use of non-crop plants for PFCs phytoremediation is promulgated due to concern of food wastage and the biomass generated from phytoremediating plants should ideally be suitable as feedstock for bioenergy production. This review contributes to further advancement of PFCs phytoremediation by addressing its current limitations.

Biological treatment of perfluorooctanesulfonic acid (PFOS) using microbial capsules of a polysulfone membrane

Perfluorooctanesulfonic acid (PFOS) is a persistent organic substance that has been extensively applied in many industries and causes severe, widespread adverse health impacts on humans and the environment. The development of an effective PFOS treatment method with affordable operational costs has been expected. This study proposes the biological treatment of PFOS using microbial capsules enclosing a PFOS-reducing microbial consortium. The objective of this study was to evaluate the performance of the polymeric membrane encapsulation technique for the biological removal of PFOS. First, a PFOS-reducing bacterial consortium, composed of Paracoccus (72%), Hyphomicrobium (24%), and Micromonosporaceae (4%), was enriched from activated sludge by acclimation and subsequent subculturing with PFOS containing media. The bacterial consortium was first immobilized in alginate gel beads, then enclosed in membrane capsules by coating the gel beads with a 5% or 10% polysulfone (PSf) membrane. The introduction of microbial membrane capsules could increase PFOS reduction to between 52% and 74% compared with free cell suspension, which reduced by 14% over three weeks. Microbial capsules coated with 10% PSf membrane demonstrated the highest PFOS reduction at 80% and physical stability for six weeks. Candidate metabolites including perfluorobutanoic acid (PFBA) and 3,3,3- trifluoropropionic acid were detected by FTMS, suggesting the possible biological degradation of PFOS. In microbial membrane capsules, the initial adsorption of PFOS on the shell membrane layer enhanced subsequent biosorption and biological degradation by PFOS-reducing bacteria immobilized in the core alginate gel beads. The 10%-PSf microbial capsules exhibited a thicker membrane layer with the fabric structure of a polymer network, which maintained longer physical stability than 5%-PSf microbial capsules. This outcome suggests the potential application of microbial membrane capsules to PFOS-contaminated water treatment.

Longer-term temporal trends in PFAS concentrations in Midwestern landfill leachate.

It is well documented that per- and polyfluoroalkyl substances (PFAS) are routinely detected in leachate from municipal solid waste (MSW) landfills. PFAS-containing products are ubiquitous in society and in end-of-life discarded materials. While considerable data have been generated in recent years for PFAS concentrations in landfill leachate, little published information exists concerning longer-term trends in leachate concentrations. In this study, we examine a ten-year dataset for three MSW landfills located in the upper Midwestern United States where leachate PFAS testing has been performed on a quarterly basis. The significance of these data are considered in light of phase-out initiatives implemented in the US manufacturing companies for longer-chain PFAS including perfluorooctanoic acid (PFOA), perfluorooctane sulphonate (PFOS) and perfluorononanoic acid (PFNA). Findings from this study indicate that the average concentration of longer-chain PFOA in the three landfills decreased from 2400 to 1900 ng/L and the average PFOS concentrations decreased from 1000 to 370 ng/L. This may be indicative of reduced domestic production and use of these compounds. The phase-out of long-chain PFAS has also led to the introduction of shorter-chain replacement compounds such as perfluorobutanoic acid, perfluorobutane sulphonate and perfluorohexanoic acid, and this paper also examines long-term trends in leachate concentrations of these compounds.

Strategy to Minimize Plant Accumulation of Contaminants of Emerging Concern: Alternation between Treated Wastewater and Freshwater Irrigation

Treated wastewater (TWW) is increasingly used for agricultural irrigation in arid and semiarid areas, but it can introduce contaminants of emerging concern (CECs) into the food chain, posing a potential risk to human health. While many studies have shown that plants can accumulate some CECs, so far little effort has been made to explore mitigation strategies. This study tested the concept of alternating between TWW with conventional freshwater for irrigation to minimize CEC accumulation in plants. Tomato and lettuce seedlings were first cultivated in CEC-containing hydroponic solutions for 3 weeks, and then in CEC-free media for another 3 weeks. The plant tissues contained elevated concentrations of perfluorobutanesulfonate, perfluorobutanoic acid, perfluorohexanoic acid, carbamazepine, and fluoxetine ranging from 42.1 to 2724.2 ng/g (dry weight). However, after being transferred to CEC-free media, most CEC levels decreased by over 75%, attributed to plant metabolism, growth dilution and back release to culture media. This proof-of-concept study suggested that using TWW during the early part of the growing season may effectively minimize CEC accumulation. Such hybrid irrigation schemes have a great prospect for expanding the safe reuse of TWW and other lower-quality water sources in agriculture and should be further evaluated under field conditions.

Validation of UV/persulfate as a PFAS treatment of industrial wastewater and environmental samples

The contamination of natural water and industrial wastewater with per- and polyfluoroalkyl substances (PFAS) occurs globally. Thus, proper technologies are required to reduce PFAS in the environment and mitigate the adverse effects of these pollutants on human health and the environment. This study used a 23 full factorial design to evaluate the importance of operating factors including the level of persulfate (PS), the initial concentration of PFAS, and the time to the photochemical degradation of PFAS via ultraviolet irradiation at 185/254 nm assisted with persulfate (PS/UV method) in spiked solution. The method was then applied to break down PFAS in industrial wastewater, landfill leachate and groundwater samples using the highest factor levels applied in the 23 full factorial design. The results showed that the three investigated factors played an important role in the degradation of PFAS. The highest PFAS degradation was 57 % perfluorobutanoic acid (PFBA), 80 % perfluorooctanoic acid (PFOA) and 60 % perfluorooctane sulfonate (PFOS) using 10 mg L−1 PFAS, 5 g L−1 PS for 4 h. The defluorination also increased in the presence of PS but decreased in the presence of potassium hydrogen phthalate, nitrates, and chlorides. The PS/UV method decreased the concentration of PFAS in wastewater samples by 20–25 % PFOS and 13–15 % perfluorohexane sulfonate (PFHxS). PFAS degradation in wastewater improved with increasing treatment time. Under the PS/UV treatment, the degradation of major PFAS in groundwater was 94 % 6–2 FTS, 75 % PFOA, 62 % PFOS and 61 % PFHxS. The removal of major compounds in landfill leachate reached up to 12 % PFHxA, 32 % PFPeA, 56 % PFOA and 43 % PFOS. Our study indicated matrix effects leading to decreased PFAS degradation in different contaminated waters. The level of PS should also be controlled to an optimal value because higher levels led to a decrease in treatment efficiency.

Pollution Characteristics and Health Risk Assessment of Per- and Polyfluoroalkyl Substances and Emerging Alternatives in Road Dust, Shijiazhuang

Per- and polyfluoroalkyl substances (PFASs, n=22), including emerging alternatives, in dust samples were analyzed using high-performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) to study their pollution characteristics. These samples were collected from main and minor roads in Shijiazhuang. Some of the roads were located near sewage treatment plants and fire stations. The results showed that PFASs were ubiquitous in the road dust of Shijiazhuang; in particular, hexafluoropropylene oxide dimer acid (HFPO-DA), an alternative, was measured for the first time in China. The total concentrations of PFASs ranged from 2.62 to 137.65 ng·g-1. Perfluorooctanoic acid (PFOA) was the dominant PFAS, followed by perfluorobutanoic acid (PFBA), HFPO-DA, and perfluorooctane sulfonic acid (PFOS). The highest and lowest levels of PFASs were observed in the northwest and southeast regions of Shijiazhuang, respectively. The compositions of PFASs were obviously different in road dust near sewage treatment plants and fire stations, especially for the types of emerging alternatives. Health risk assessment indicated that road dust intake had a low risk of human exposure to PFASs and emerging alternatives. Among the three routes (ingestion intake, inhalation intake, and dermal contact), ingestion intake was the main route for PFASs and emerging alternatives in road dust to enter the human body. Under the same exposure route, the exposure dose of children was higher than that of adults.

Adsorption of PFOS onto graphite intercalated compound and analysis of degradation by-products during electro-chemical oxidation

Perfluorooctane sulfonate (PFOS) is a highly recalcitrant perfluoro chemical belonging to the family of per- and polyfluoroalkyl substances (PFAS). Its adsorption and degradation was demonstrated in a novel PFAS remediation process involving the adsorption onto graphite intercalated compounds (GIC) and the electrochemical oxidation. The Langmuir type of adsorption was characterized by a loading capacity of 53.9 μg PFOS g−1 GIC and a second order kinetics (0.021 g μg−1 min−1). Up to 99% of PFOS was degraded in the process with a half-life of 15 min. The breakdown by-products included short chain perfluoroalkane sulfonates such as Perfluoroheptanesulfonate (PFHpS), Perfluorohexanesulfonate (PFHxS), Perfluoropentanesulfonate (PFPeS) and Perfluorobutanesulfonate (PFBS), but also short chain perfluoro carboxylic acids such as perfluorooctanoic acid (PFOA), perfluorohexanoic acid (PFHxA) and perfluorobutanoic acid (PFBA) indicating different degradation pathways. These by-products could also be broken down but the shorter the chain the slower the degradation rate. This novel combined adsorption and electrochemical process offers an alternative treatment for PFAS contaminated waters.

Enhanced adsorption of short-chain perfluorobutanoic acid by functionalized periodic mesoporous organosilica: Performance and mechanisms

Removal of short-chain per- and polyfluoroalkyl substances (PFAS) represents a unique challenge in comparison to the long-chain homologs. In this study, a series of functionalized periodic mesoporous organosilica (PMO) materials with tunable molar ratio of fluoroalkyl to amine functional groups were developed and used as platform adsorbents to investigate the adsorption behavior of short-chain PFAS, with a focus on perfluorobutanoic acid (PFBA). Modification with fluoroalkyl group substantially enhanced the adsorption affinity of PFBA with the functionalized PMO materials. Adsorption free energy analysis suggested that although electrostatic interactions were more predominant in PFBA adsorption, modification of PMOs with increased fluoroalkyl group loadings increased the non-electrostatic interactions with PFBA, resulting in more favorable PFBA adsorption. The optimal functionalized PMO showed fast PFBA adsorption kinetics, excellent PFBA removal efficiency in various water chemistry conditions, and can be regenerated and reused for numerous cycles with methanol/water mixture containing 500-mM NH3·H2O as regenerant. Furthermore, the optimal functionalized PMO showed robust performance for the removal of PFAS mixtures under complex natural water matrix. Results of this study suggested the important role of non-electrostatic interactions in enhancing the removal of short-chain PFAS and can provide mechanistic insights into guiding the design of improved adsorbents for PFAS removal.

Foam fractionation for removal of per- and polyfluoroalkyl substances: Towards closing the mass balance

Foam fractionation has recently attracted attention as a low-cost and environmentally benign treatment technology for water contaminated with per- and polyfluoroalkyl substances (PFAS). However, data on the mass balance over the foam fractionation process are scarce and when available, gaps in the mass balance are often identified. This study verified the high treatment efficiency of a pilot-scale foam fractionation system for removal of PFAS from industrial water contaminated with aqueous film-forming foam. ΣPFAS removal reached up to 84 % and the removal of perfluorooctane sulfonic acid (PFOS) up to 97 %, but the short-chain perfluorobutanoic acid (PFBA) was only removed with a mean efficiency of 1.5 %. In general, mobile short-chain PFAS were removed less efficiently when the perfluorocarbon chain length was below six for carboxylic acids and below five for sulfonic acids. Fluctuations in treatment efficiency due to natural variations in the chemistry of the influent water were minor, confirming the robustness of the technology, but significant positive correlations between PFAS removal and influent metal concentration and conductivity were observed. Over all experiments, the mass balance closure did not differ significantly from 100 %. Nonetheless, PFAS sorption to the walls of the reactor was measured, as well as high PFAS emissions by the air exiting the reactor. PFAS emissions in aerosols correlated positively with mass balance closure. The elevated aerial PFAS concentrations measured in the experimental facility have implications for worker safety and prevention of PFAS-emissions to the atmosphere, and demonstrate the importance of installing appropriate filters on the air outlet of foam fractionation systems.