Heptafluorobutyric Acid Research Articles

Detection of Per- and Polyfluoroalkyl Substances in High-Protein Food Products.

Per- and polyfluoroalkyl substances (PFAS) belong to the emerging class of persistent organohalogenated contaminants in the environment. We determined the levels of 10 PFAS in selected samples representing different food types, with a special focus on those rich in protein such as fish, meat and meat preparations, liver, eggs, and leguminous vegetables. Such determinations were based on the Quick Easy Cheap Effective Rugged Safe extraction procedure followed by micro-high-performance liquid chromatography-tandem mass spectrometry. The most frequently found was perfluorooctanoic acid, in 84% of the food samples. However, its maximum measured concentration was 0.50 ng g-1 , in a herring sample. The highest concentrations were for perfluorobutanoic acid (35 ng g-1 measured in a pork liver sample) and perfluorooctane sulfonate (12 ng g-1 measured in a herring sample). Because these compounds may bioaccumulate in human tissues by dietary intake, further research into their impact on human health is called for. Environ Toxicol Chem 2023;42:2589-2598. © 2023 SETAC.

Legacy and emerging per- and polyfluoroalkyl substances (PFAS) regulate steroidogenesis in the male gonad.

Per- and polyfluoroalkyl substances (PFAS) are widely used in a variety of industrial processes and manufacturing of consumer products. Current efforts by the manufacturing industry will limit use of long-chain or legacy PFAS represented by perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS) and replace with short-chain or emerging PFAS such as perfluorobutanoic acid (PFBA) and perfluorobutane sulfonic acid (PFBS). However, there is little to no information on the toxicity of new and emerging PFAS. Therefore, we performed experiments in growing Long-Evans male rats to investigate effects of low dose prepubertal and pubertal exposures to PFAS on gonadal steroid hormone secretion. The results demonstrated that both legacy and emerging PFAS have the capacity to regulate testicular steroidogenesis. For example, prepubertal exposures to PFOS, PFBA and PFBS increased serum and testicular T concentrations. Exposure to PFBA increased testicular E2 concentrations and PFOS and PFBS both decreased serum E2 concentrations while stimulating testicular E2 secretion. The data also demonstrated additive effects due to legacy and emerging PFAS mixtures compared to the individual chemicals. The gonadal effects due to PFAS exposures occurred at nanomolar concentrations, which approximate PFAS levels in the environment. Taken together, the present study support the need for development of cost-effective and sustainable filtration media for different processes to remove PFAS from water and other sources of exposure. Current action by regulatory agencies such as the US Environmental Protection Agency to limit use of PFAS in the manufacture of consumer products will protect public health.

Effects of drinking water treatment residual amendments to biosolids on plant uptake of per- and polyfluoroalkyl substances.

Drinking water treatment residuals (DWTRs), solid by-products of drinking water treatment, are dominated by calcium (Ca), iron (Fe), or aluminum (Al), depending on the coagulant used. DWTRs are often landfilled, but current research is exploring options for beneficial reuse. Previous studies have shown that Al- and Fe-rich materials have potential to reduce the mobility of per- and polyfluoroalkyl substances (PFAS). Here, we investigated how amending biosolids with 5%wt/wt DWTRs affected plant bioavailable PFAS in two different simulated scenarios: (1) agricultural scenario with Solanum lycopersicum (tomato) grown in soil amended with an agronomically relevant rate of DWTR-amended biosolids (0.9% w/w, resulting in 0.045% w/w DWTR in the biosolids-amended soil) and (2) mine reclamation scenario examining PFAS uptake by Lolium perenne (perennial ryegrass) grown in soil that received DWTR-amended biosolids amendment at a rate consistent with the mine remediation (13% w/w, resulting in 0.65% w/w DWTR in the biosolids-amended soil). Amending biosolids with Ca-DWTR significantly reduced perfluorobutanoic acid (PFBA) uptake in ryegrass and perfluorohexanoic acid uptake in tomatoes, possibly due to DWTR-induced pH elevation, while Fe-DWTR amendment reduced PFBA bioaccumulation in ryegrass. The Al-DWTR did not induce a significant reduction in accumulated PFAS compared to controls. Although the reasons for this finding are unclear, the relatively low PFAS concentrations in the biosolids and relatively high Al content in the biosolids and soil may be partially responsible.

Chemical Tailoring of β-Cyclodextrin-Graphene Oxide for Enhanced Per- and Polyfluoroalkyl Substances (PFAS) Adsorption from Drinking Water.

We report on the synthesis of β-cyclodextrin (βCD) modified graphene oxide (GO) nanosheets, having different sized alkyl linkers (GO-Cn -βCD) and their exploitation as sorbent of per- and polyfluoroalkyl substances (PFAS) from drinking water. βCD were functionalized with a pending amino group, and the resulting precursors grafted to GO nanosheets by epoxide ring opening reaction. Loading of βCD units in the range 12 %-36 % was estimated by combined XPS and elemental analysis. Adsorption tests on perfluorobutanoic acid (PFBA), a particularly persistent PFAS selected as case study, revealed a strong influence of the alkyl linker length on the adsorption efficiency, with the hexyl linker derivative GO-C6 -βCD outperforming both pristine GO and granular activated carbon (GAC), the standard sorbent benchmark. Molecular dynamic simulations ascribed this evidence to the favorable orientation of the βCD unit on the surface of GO which enables a strong contaminant molecules retention.

Separation and quantification of Azvudine in plasma of patients with COVID-19 using LC-MS/MS

Azvudine (FNC) is a new drug conditionally approved in 2022 for the treatment of coronavirus disease 2019 (COVID-19) in China. However, the exposure level of FNC in COVID-19 patients in clinical practice is still obscure, and there is no liquid chromatography-tandem mass spectrometry (LC-MS/MS) or LC method reported for quantifying the FNC. In this study, a simple, fast, and reliable LC-MS/MS method using L-phenylalanine-D5 (Phe-D5) as the internal standard (IS) was developed for the quantification of FNC in plasma from COVID-19 patients. After simple protein precipitation with methanol, the analyte in the supernatant was separated on Waters Atlantis® T3 (2.1 ×100 mm, 3.0 µm) column with the mobile phase consisting of acetonitrile (ACN) - aqueous solution (containing 0.03% heptafluorobutyric acid and 0.2% formic acid). The mobile phase was delivered at 0.3 mL/min in an isocratic elution program (15:85, V: V). The linear relationship of FNC was good within the calibration range of 2.0 – 2000.0 ng/mL, with the recovery of FNC ranging from 81.37% to 103.31% and the matrix effect was 94.77%− 109.83%. The short-term, long-term, and freeze-thaw stability of the FNC assessed in method was acceptable, and all other items met the requirements of validation of the biological analytical method. Finally, the method was applied to detect the exposure level of FNC in plasma samples from patients diagnosed with COVID-19, and the results, which are within the linear range of the method, showed huge inter-individual variation, supporting the significance of therapeutic drug monitoring of FNC.

Bioaccumulation, tissue distributions, and maternal transfer of perfluoroalkyl carboxylates (PFCAs) in laying hens

Laying hens were exposed to feeds spiked with a series of perfluoroalkyl carboxylates (PFCAs) ranging from perfluorobutanoic acid (C4) to perfluorooctadecanoic acid (C18) to investigate their bioaccumulation, tissue distribution, and maternal transfer. We found that PFCAs with longer carbon chains (>8) were more efficiently absorbed in the gastrointestinal tract than those with shorter chains (≤8), and that the rate of depuration varied inversely with the carbon chain length in a U-shaped pattern. Moreover, bioaccumulation potential increased with increasing carbon-chain length, except for C4. Distinct affinities were observed for specific carbon-chain PFCAs across various tissues, evident from their differential accumulation during both uptake and depuration phases. Specifically, C9 showed a higher affinity for serum and liver, C12 was more prevalent in yolk, C14 was notably abundant in the brain, and C18 was predominant in other tissues. Furthermore, the egg-maternal ratio (EMR) increased with increasing carbon-chain length from C7 to C11 and reached a plateau phase for C12 to C18. Our study also confirmed the key role of phospholipids in the tissue distribution and maternal transfer of long-chain PFCAs. This study sheds light on the interaction between PFCAs and biological tissues and reveals the toxicokinetic factors that influence the bioaccumulation of PFCAs. Further research is needed to identify the specific proteins or components that mediate the tissue-specific affinity for different carbon-chain lengths of PFCAs.

Presence of Perfluoroalkyl Carboxylic Acids and Sulfonates in Vietnamese Food Contact Materials

Per- and polyfluoroalkyl substances (PFASs) are considered as persistent organic pollutants (POPs), which should be restricted or eliminated. In this study, concentrations of four perfluoroalkyl carboxylic acids (perfluorobutanoic acid PFBA, perfluorohexanoic acid PFHxA, perfluorooctanoic acid PFOA, perfluorodecanoic acid PFDA) and four perfluoroalkyl sulfonates (perfluorobutane sulfonate PFBS, perfluorohexane sulfonate PFHxS, perfluorooctane sulfonate PFOS, perfluorodecane sulfonate PFDS) were analyzed in food contact materials (FCM) collected from Hanoi, Vietnam. A total of 15 FCM samples was obtained including several categories such as instant drink/food boxes, bags, cups, wrappers, and tray. The FCM samples were untrasonic extracted with methanol, concentrated, and filtered before analysis by a liquid chromatography–tandem mass spectrometry (LC-MS/MS) system. Recoveries of native and surrogate standards ranged from 70% to 130% with RSD < 20% in replicated analysis. Method detection limits of PFASs ranged from 0.04 to 0.08 ng/g. Concentrations of S8PFASs ranged from not detected (ND) to 1.46 (average ± SD: 0.417 ± 0.479) ng/g. Detection frequencies of PFASs decreased in the order: PFDA (33%) > PFBA, PFOA, PFHxS, PFOS (27%) > PFDS (13%) > PFHxA (7%) > PFBS (0%). Average concentrations of individual compounds decreased in the order: PFOS > PFDA > PFHxS > PFOA > PFBA > PFHxA > PFDS > PFBS. Relatively low PFAS concentrations found in the FCM samples of this study indicated that these substances were mainly derived from unintentional sources rather than intentionally added to the materials.

Determination of underivatized amino acids in human plasma using ion pair liquid chromatography/tandem mass spectrometry

Accurate quantification of amino acids (AA) is essential for several applications, including clinical research, food analysis, and pharmaceutical studies. In this study, we developed an analytical method based on liquid chromatography with electrospray ionization coupled to tandem mass spectrometry detection (LC-ESI-MS/MS). This method was devised to accurately quantify a spectrum of amino acids, notably taurine, creatinine, glutathione (GSH), and sulfur-containing amino acids (SAAs) such as methionine, cysteine, and homocysteine, using only 10 μL of human plasma. A stable isotope derivative of each AA is used as an internal standard (IS) for accurate quantification. For retention and separation on a C18 column, heptafluorobutyric acid (HFBA) was employed as an ion pair agent. Multiple reaction monitoring (MRM) in positive mode with the precursor-to-product ion transitions at m/z is used for quantification. The method showed excellent linearity for all AA with a high correlation coefficient (r > 0.9927). The linear fit indicates that the detector response is linear over the tested range of standard concentrations. The accuracy and precision of the method were within the acceptable range of 92–110% and < 15%, respectively. The limit of detection (LOD) and limit of quantification (LOQ) were in the range of 0.001–1.80 µM and 0.004–6.0 µM, respectively. No significant ion suppression or carry over was observed. In conclusion, the assay was validated and found to have adequate accuracy, precision, linearity, sensitivity and selectivity. The assay has been successfully applied to the analysis of human plasma.

Removal of short- and long-chain PFAS from aquatic systems using electrostatic attraction of polyethylenimine-polyvinyl chloride electrospun nanofiber adsorbent

The presence of per- and polyfluoroalkyl substances (PFAS) in the water environment raises serious concerns due to their persistence and toxicity that links to adverse health consequences. Short-chain PFAS are more challenging to remove from water by adsorption than long-chain PFAS due to the weaker hydrophobic interaction, and conventional adsorbents usually demonstrated poor PFAS adsorption capacities near neutral pH. We have examined a novel polyethylenimine-polyvinyl chloride electrospun nanofiber (PEI-PVC NF) adsorbent to improve the adsorption capacity of both short- [perfluorobutanoic acid (PFBA) and perfluorobutanesulfonic acid (PFBS)] and long-chain [perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS)] PFAS by maximizing electrostatic attraction using a PEI functional group with nanopore structure. At pH 7, PEI-PVC NF demonstrated adsorption capacities of 84.26 mg/g for PFBA and 214.37 mg/g for PFBS (short-chain PFAS), and 213.76 mg/g for PFOA and 326.39 mg/g for PFOS (long-chain PFAS). These adsorption capacities were only 20.1–61.3% lower than those obtained under acidic conditions. Excellent adsorption capacities by PEI-PVC NF are likely due to the strong electrostatic attraction with PEI under acidic to neutral pHs as well as pore-mediated adsorption driven by nanopore structure. The isotherm adsorption data were well fitted with the Langmuir model, which supports dominant monolayer adsorption driven by electrostatic attraction. Maximum adsorption capacities (qmax, 98.70 mg/g for PFBA, 222.36 mg/g for PFBS, 234.85 mg/g for PFOA, and 319.82 mg/g for PFOS) were superior to adsorbents that were previously reported at pH 7. Adsorption kinetic tests demonstrated remarkable PFAS adsorption rates (reached equilibrium in 300 min) by PEI-PVC NF likely driven by electrostatic and intraparticle diffusion into nanopores.

Human health risk-based soil generic assessment criteria of representative perfluoroalkyl acids (PFAAs) under the agricultural land use in typical Chinese regions

Perfluoroalkyl acid substances (PFAAs), such as perfluorobutanoic acid (PFBA), perfluorobutanoic sulfonic acid (PFBS), perfluorooctane acid (PFOA) and perfluoroooctane sulfonic acid (PFOS) are frequently detected in the global environment and can cause potential health hazards even at low levels. In this study, quantitative human health risk assessment was undertaken to derive soil generic assessment criteria (GAC) for four PFAAs under the agricultural land scenario in the evaluated Chinese regions, which considered multiple exposure pathways including vegetables consumption, dermal absorption, ingestion of soil and dust, and exposure from non-soil sources. It is showed that the calculated GAC for four PFAAs in Guangdong and Shandong Provinces were less stringent than those in Zhejiang and Jiangsu Provinces, and Shanghai City, owing to the low exposure from non-soil sources in former two provinces. In addition, GAC of PFOS were the most stringent in the range of 0.28–0.50 μg kg−1 in the studied regions, followed by PFOA (1.36–2.20 μg kg−1), PFBA (42.59–68.03 μg kg−1) and PFBS (474.59–749.60 μg kg−1), mainly attributable to significantly more stringent toxicological values of PFOA and PFOS. Correspondingly, the potential health hazards exist for PFOA in the studied regions except Guangdong Province, and PFOS only in Zhejiang and Jiangsu Provinces as indicated by the hazard quotients ranging from 1.04 to 19.49, but no health hazards are identified for PFBA and PFBS. The dominant exposure pathway was found to be consumption of vegetables and attached soil for PFBA and PFBS, contributing to more than 93% of the total exposure, compared to 49.91–76.69% for PFOA and PFOS due to significant exposure from non-soil sources levels. Overall, this study provides a technical reference on how to derive scientifically justifiable soil GAC for representative PFAAs for maintaining and assessing soil quality and food safety internationally under the agricultural land use.

Application of in-source fragmentation to the identification of perfluoropentanoic acid and perfluorobutanoic acid in environmental matrices and human serum by isotope dilution liquid chromatography coupled with tandem mass spectrometry

Liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) is the most common analytical technique for per- and polyfluoroalkyl substances (PFASs) research and monitoring. The PFAS identification requires a minimum of two multiple reaction monitoring (MRM) transition ions as quantifier transition ion and qualifier transition ion, respectively. The second transition ion abundance for perfluoropentanoic acid (PFPeA) and perfluobutanoic acid (PFBA) is too low for practical use. A method using the in-source fragment ions as the precursor ion for MRM or pseudo-MRM has been developed and evaluated for PFPeA and PFBA identification in various environmental abiotic and biotic samples including water, soil, sediment, WWTP sludge, fruits, vegetables, egg, macrophytes, fish, dolphin liver and human serum. The PFPeA qualifier MRM transition ion (m/z = 219 > 69) has been successfully applied in all the matrices with spike recoveries (90–125%), signal to noise ratios (>10) and transition ions ratio variation (80–120%). The PFBA qualifier pseudo-MRM transition ion (m/z = 169 > 169) works well in all the matrices except dolphin liver sample. The interpretation of pseudo-MRM results should be with cautions due to lower specificity compared to MRM. In addition, this project indicated under typical chromatographic conditions the MRM isobaric interference does happen frequently to PFPeA quantifier transition ion (m/z = 263 > 219) in serum and fish composite samples, and to PFBA quantifier transition ion (m/z = 213 > 169) in macrophytes, fish composite and dolphin liver samples.

In situ self-sacrificial synthesis of polypyrrole/biochar composites for efficiently removing short- and long-chain perfluoroalkyl acid from contaminated water

Efficient removal of perfluoroalkyl acids (PFAAs), especially short-chain ones, from contaminated water is of great challenge and is urgently called for so as to safeguard the ecosystem and human health. Herein, polypyrrole (PPy) functionalized biochar (BC) composites were innovatively synthesized by an in situ self-sacrificial approach to allow efficient capture of PFAAs with different chain lengths. Compared with conventional PPy-based composites synthesized by direct polymerization using FeCl3 as an oxidizing agent, PPy/BC composites were fabricated utilizing freshly generated Fe3+ as an oxidizing agent from self-sacrificial Fe3O4 for pyrrole monomers in situ polymerizing on BC. As a result, with the support of BC and gradual release of Fe3+, PPy overcame its tendency to aggregate and became uniformly dispersed on BC, and meanwhile, PPy could well tailor the surface chemistry of BC to endow its positively charged surface. Consequently, the composites exhibited strong sorption capacities of 3.89 and 1.53 mmol/g for short-chain perfluorobutanoic acid (PFBA) and perfluorobutane sulfonic acid (PFBS), 2.55 and 1.22 mmol/g for long-chain perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), respectively, which were superior to those of pristine BC, commercial activated carbon, and anion exchange resins reported. Additionally, they could effectively remove 17 different classes of per- and polyfluoroalkyl substances (PFAS) (removal >95%) from actual PFAS-contaminated water, and the spent sorbent could be well regenerated and reused at least 5 times. An integrated analysis indicated that such an outstanding PFAA sorption performance on PPy/BC composites could be mainly attributed to surface adsorption enhanced by electrostatic attractions (anion exchange interaction) with the traditional hydrophobic interaction and pore filling of less contribution, particularly for short-chain analogues. These results are expected to inform the design of BC with greater ability to remove PFAS from water and the new sorbent could help water facilities comply with PFAS regulations.

Occurrence of metals, phthalate esters, and perfluoroalkyl substances in cellar water and their relationship with bacterial community in rural areas of China

Water cellars are traditional rainwater harvesting facilities that have been widely used in rural areas of northwest China. However, there are few reports about the water quality and health risk caused by the cellar water, especially phthalate esters (PAEs) and perfluoroalkyl substances (PFASs). This study investigated and assessed the health risks caused by the metals, PAEs, PFASs and bacterial communities in cellar water. The results showed that the turbidity and total number of bacterial colonies ranged from 4.7 to 58.5 NTU and 5–557 CFU/mL, respectively. The turbidity and total number of bacterial colonies were the main water quality problems. Due to high concentration of Tl (0.005–0.171 μg/L), the samples reached a high level of metal pollution. PAEs showed no non-carcinogenic and carcinogenic risk. The perfluorobutanoic acid (PFBA), perfluorobutanesulfonic acid (PFBS), perfluorooctanoic acid (PFOA), and perfluorooctane sulfonate (PFOS) were the main components of PFASs. PFOA and PFOS reached a moderate risk level in many cellar water samples. Moreover, Tl, Pb, As, PFBA and PFBS could change the bacterial community composition and induce the enrichment of bacterial functions related to human diseases. Besides these parameters, dissolved oxygen (DO) also affected the bacterial functions related to human diseases. Therefore, more attention should be paid to turbidity, DO, Tl, Pb, As, PFOA, PFOS, PFBA and PFBS in the cellar water. These results are meaningful for the water quality guarantee and health protection in rural areas of China.

Enhanced PFAS adsorption with N-doped porous carbon beads from oil-sand asphaltene

Highly porous carbon beads with radially aligned macrochannels were synthesized from asphaltene for wastewater treatment and water filtration purposes. The unique porous structure of these beads facilitates efficient solute diffusion and maximizes liquid accommodation capacity, thanks to the well-ordered inwardly aligned macrovoids. Additionally, N-doping was employed to enhance the beads' adsorption properties, particularly for organic and inorganic solvents. Surface characterization data revealed that N2 modification introduced new surface functionalities, likely pyridine, and amine moieties, which actively participate in the adsorption process of polyfluoroalkyl and perfluoroalkyl substances (PFAS). Although the highest adsorbed amount of up to 74 μmol g−1 was observed for the unmodified materials, it is noteworthy that achieving equilibrium required an extensive period, exceeding 300 h. Interestingly, adsorption onto N2-modified asphaltene carbon beads exhibited higher efficiency for shorter-chain PFAS, with perfluorobutanoic acid adsorbing at 66.41 μmol g−1 and perfluorooctanoic acid reaching up to 7.67 μmol g−1. Overall, the maximum adsorption capacity of all asphaltene carbon beads followed the order PFHxA < PFOA < PFBA, indicating that the length of the carbon chain in PFAS is not the sole determining factor for adsorption. This observation suggests that the modification of asphaltene carbon beads and the introduction of N2 in the form of amino groups provide additional sites for hydrogen bond formation, influencing the adsorption process. The presented results highlight the enhanced efficiency of PFAS removal achieved by utilizing sustainable materials and methods in wastewater treatment.

Environmental exposure and ecological risk of perfluorinated substances (PFASs) in the Shaying River Basin, China

There have been concerns raised about the environmental effects of perfluoroalkyl substances (PFASs) because of their toxicity, widespread distribution, and persistence. Understanding the occurrences and ecological risk posed by PFASs is essential, especially for the short-chain replacements perfluorobutanoic acid (PFBA) and perfluorobutane sulfonic acid (PFBS), which are now becoming predominant PFASs. The lack of aquatic life criteria (ALC), however, prevents an accurate assessment of the ecological risks of PFBA and PFBS. This study thus investigated the occurrence of 15 PFASs at 29 sampling sites in Shaying River Basin (in China) systematically, conducted the toxicity tests of PFBA and PFBS on eight resident aquatic organisms in China, and derived the predicted non-effect concentration (PNEC) values for PFBA and PFBS for two environmental media in China. The results showed that the total PFASs concentrations (ΣPFASs) ranged from 5.07 to 20.32 ng/L (average of 10.95 ng/L) in surface water, whereas in sediment, ΣPFASs ranged from 6.46 to 20.05 ng/g (dw) (average of 11.51 ng/g). The presence of PFBS was the most prominent PFASs in both water (0.372–8.194 ng/L) and sediment (4.54–15.72 ng/g), demonstrating that short-chain substitution effects can be observed in watersheds. The PNEC values for freshwater and sediment were 6.60 mg/L and 8.30 mg/kg (ww), respectively, for PFBA, and 14.04 mg/L, 37.08 mg/kg (ww), respectively, for PFBS. Ecological risk assessment of two long-chain PFASs, perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS), and two short-chain PFASs, PFBA and PFBS, using the hazard quotient method revealed that Shaying River and other major River Basins in China were at risk of PFOS contamination. This study contributes to a better understanding of the presence and risk of PFASs in the Shaying River and first proposes the ALCs for PFBA and PFBS in China, which could provide important reference information for water quality standards.

Analysis of ultrashort-chain and short-chain (C1 to C4) per- and polyfluorinated substances in potable and non-potable waters

Ultrashort-chain (USC) per- and polyfluoroalkyl substances (PFAS) are small and very polar compounds with carbon chain lengths of less than C4. Their ubiquitous occurrence in aquatic environments has become a major concern in parallel to long chain PFAS contamination. The high polarity of USC PFAS challenges current analytical practices based on reversed-phase liquid chromatography due to insufficient chromatographic retention. In this study, a fast and reliable LC-MS/MS method was developed for the analysis of C1 to C4 PFAS including trifluoroacetic acid (TFA), perfluoropropanoic acid (PFPrA), perfluorobutanoic acid (PFBA), trifluoromethanesulfonic acid, perfluoroethanesulfonic acid, perfluoropropanesulfonic acid, and perfluorobutanesulfonic acid utilizing a hybrid HILIC/ion exchange column. Three different water samples (tap water, bottled spring water, sewage treatment wastewater) were chosen for method validation to demonstrate the applicability of developed analytical method for the measurement of C1 to C4 PFAS in both potable and non-potable waters. A direct injection workflow was evaluated by accuracy and precision analysis of fortified water samples. Accurate quantification was achieved using calibration standards prepared in reverse osmosis water at the range of 20 to 800 ng/L for TFA, 5.0 to 800 ng/L for PFPrA and PFBA, and 2.5 to 800 ng/L for sulfonic acid PFAS. The average recoveries of fortified samples among three water samples were from 86.6% to 107%, and the relative standard deviation ranged from 1.62% to 10.7%. Additional drinking waters and wastewaters collected from various source waters were tested to further demonstrate that the established workflow is suitable for accurate quantification of C1 to C4 PFAS in a variety of water matrices.

The effect of green sorption media pretreatment on nanofiltration during water treatment for long- and short-chain per- and polyfluoroalkyl substances (PFAS) removal

Short-chain per- and polyfluoroalkyl substances (PFAS) have higher mobility than long-chain PFAS. This study investigated the application potential of two specialty adsorbents as pretreatment media for nanofiltration (NF) to enhance the removal of both short- and long-chain PFAS from water matrices. In this hybrid process, two specialty adsorbents, known as green sorption media (GSM), were prepared using recycled and natural materials for cost-effective, scalable, and sustainable water pretreatment. These two GSM are named the clay-perlite and sand (CPS) sorption media and zero-valent iron and perlite-based green environmental media (ZIPGEM). Such pretreatment led to significant removal of long-chain PFAS (up to 100 %) in addition to natural organic matter (NOM) and Ca2+ from the source water (canal water); however, for the short-chain PFAS (Perfluorobutanoic acid and Perfluorobutanesulfonic acid), the removal rate only rose to approximately 25 %. Such a contrasting removal rate is attributable to the source water concentration of PFAS and the hydrophobic and electrostatic interactions of the compounds within the treatment media. Yet the CPS–NF and ZIPGEM–NF hybrid processes exhibited significantly higher removal of perfluorooctanesulfonic acid (long-chain PFAS; approximately 16 % higher) when compared to the control (i.e., NF only). Because the pretreatment media removed higher percentages of long-chain PFAS, NOM, and Ca2+ from the water, the performance of the subsequent NF declined due to less calcium bridging involving NOM and PFAS and less micelle/complex formation by the compounds in bulk water. However, the integration of GSM with NF significantly improved (up to approximately 25 % higher) PFAS removal efficiency via the hybrid functionality. This signifies the membrane plays a complementary role in enhancing the overall removal efficiency of PFAS. In addition to contributing to PFAS removal from the source water, GSM pretreatment can help reduce NF membrane fouling/scaling by removing NOM and cations.

First Investigation of the Physiological Distribution of Legacy and Emerging Perfluoroalkyl Substances in Raw Bovine Milk According to the Component Fraction.

Bovine milk is a pillar of the human diet and plays a key role in the nutrition of infants. Perfluoroalkyl substances (PFASs) are well-recognized highly stable organic compounds that are able to pollute ecosystems persistently and threaten both human and animal health. The study aimed to analyze the distribution of 14 PFASs within the milk matrix by comparing their content in whole milk, and its skimmed and creamed fractions. Raw milk samples were individually collected from 23 healthy cows (10 primiparous and 13 multiparous) reared on a farm in Northern Italy not surrounded by known point sources of PFASs. Each sample was fractioned in whole, skim, and cream components to undergo PFAS analysis using liquid chromatography-high-resolution mass spectrometry. All samples contained at least one PFAS, with perfluorobutanoic acid (PFBA) being the primary contaminant in all three fractions, followed by perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA). PFOS was shown to be significantly (p < 0.001) more concentrated in cream than in raw and skimmed milk. Multiparous cows showed a higher frequency of positive samples in all analyzed fractions. Further research is necessary to assess the risk of dairy diets and high-fat dairy products and to investigate the toxicological effects of PFASs on cattle, even in environments without known PFAS sources.

The in situ treatment of PFAS within porewater at the air–water interface of a PFAS source zone

AbstractThe treatment of per‐ and polyfluoroalkyl substances (PFAS) within groundwater is an emerging topic, with various technologies being researched and tested. Currently, PFAS‐impacted groundwater is typically treated ex situ using sorptive media such as activated carbon and ion exchange resin. Proven in situ remedial approaches for groundwater have been limited to colloidal activated carbon (CAC) injected into aquifers downgradient of the source zones. However, treatment of groundwater within the source zones has not been shown to be feasible to date. This study evaluated the use of CAC to treat dissolved PFAS at the air–water interface within the PFAS source zone. Studies have shown that PFAS tends to preferentially accumulate at the air–water interface due to the chemical properties of the various PFAS. This accumulation can act as a long‐term source for PFAS, thus making downgradient treatment of groundwater a long‐term requirement. A solution of CAC was injected at the air–water interface within the source zone at a site with PFAS contamination using direct push technology. A dense injection grid that targeted the interface between the air and groundwater was used to deliver the CAC. Concentrations of PFAS within the porewater and groundwater were collected using a series of nine lysimeters installed within the vadose and saturated water columns. A total of six PFAS were detected in the porewater and groundwater including perfluorobutanoic acid (PFBA), perfluoropentanoic acid (PFPeA), perfluorohexanoic acid (PFHxA), perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), and perfluorononanoic acid (PFNA). Detectable concentrations of PFAS within the pore and groundwater before treatment ranged from values greater than 300 µg/L for PFPeA to less than 3 µg/L for PFNA. Following the injection of the CAC, monitoring of the porewater and groundwater for PFAS was conducted approximately 3, 6, 9, 12, and 18 months postinjection. The results indicated that the PFAS within the porewater and groundwater at and near the air–water interface was effectively attenuated over the 1.5‐year monitoring program, with PFAS concentrations being below the method detection limits of approximately 10 ng/L, with the exception of PFPeA, which was detected within the porewater during the 18‐month sampling event at concentrations of up to 55 ng/L. PFPeA is a five carbon‐chained PFAS that has been shown to have a lower affinity for sorption onto activated carbon compared to the longer carbon‐chained PFAS such as PFOA. Examination of aquifer cores in the zone of injection indicated that the total organic carbon concentration of the aquifer increased by five orders of magnitude postinjection, with 97% of the samples collected within the target injection area containing activated carbon, indicating that the CAC was successfully delivered into the source zone.

Electrosorption, Desorption, and Oxidation of Perfluoroalkyl Carboxylic Acids (PFCAs) via MXene-Based Electrocatalytic Membranes.

MXenes exhibit excellent conductivity, tunable surface chemistry, and high surface area. Particularly, the surface reactivity of MXenes strongly depends on surface exposed atoms or terminated groups. This study examines three types of MXenes with oxygen, fluorine, and chlorine as respective terminal atoms and evaluates their electrosorption, desorption, and oxidative properties. Two perfluorocarboxylic acids (PFCAs), perfluorobutanoic acid (PFBA) and perfluorooctanoic acid (PFOA) are used as model persistent micropollutants for the tests. The experimental results reveal that O-terminated MXene achieves a significantly higher adsorption capacity of 215.9 mg·g-1 and an oxidation rate constant of 3.9 × 10-2 min-1 for PFOA compared to those with F and Cl terminations. Electrochemical oxidation of the two PFCAs (1 ppm) with an applied potential of +6 V in a 0.1 M Na2SO4 solution yields >99% removal in 3 h. Moreover, PFOA degrades about 20% faster than PFBA on O-terminated MXene. The density functional theory (DFT) calculations reveal that the O-terminated MXene surface yielded the highest PFOA and PFBA adsorption energy and the most favorable degradation pathway, suggesting the high potential of MXenes as highly reactive and adsorptive electrocatalysts for environmental remediation.