Perfluorinated Alkyl Substances Research Articles

Genetically Engineered Bacterial Biosensor for Detection of PFOA and PFOS in Water Samples

Several techniques were developed for identifying and quantifying Perfluorinated alkyl substances (PFASs). However, high cost, tedious procedures for separation before analysis and limited sensitivity are the limiting constraints of the existing PFAS sensors. Hence, there is a need to develop simple, low-cost and effective sensors for detecting emerging pollutants called perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS). An attempt was made to develop genetically modified bacterial biosensor system for the detection of PFOA and PFOS in water samples. The biosensor response was achieved from 10 ng/L to 10 ppm of PFOA and PFOS compounds with 24 h incubation time. The biosensor was successfully applied for the detection of PFOA or/and PFOS in different water samples and the results agree well with those results obtained by liquid chromatograph-mass spectrometer. Therefore, the developed biosensor system can be utilized for monitoring PFOA and PFOS compounds in the water samples such as pond, Lake, River and wastewater.

Critical new insights into the interactions of hexafluoropropylene oxide-dimer acid (GenX or HFPO-DA) with albumin at molecular and cellular levels

A key characteristic to be elucidated, to address the harmful health risks of environmental perfluorinated alkyl substances (PFAS), is their binding modes to serum albumin, the most abundant protein in blood. Hexafluoropropylene oxide-dimer acid (GenX or HFPO-DA) is a new industrial replacement for the widespread linear long-chain PFAS. However, the detailed interaction of new-generation short-chain PFAS with albumin is still lacking. Herein, the binding characteristics of bovine serum albumin (BSA) to GenX were explored at the molecular and cellular levels. It was found that this branched short-chain GenX could bind to BSA with affinity lower than that of legacy linear long-chain perfluorooctanoic acid (PFOA). Site marker competitive study and molecular docking simulation revealed that GenX interacted with subdomain IIIA to form BSA-GenX complex. Consistent with its weaker affinity to albumin protein, the cytotoxicity of branched short-chain GenX was less susceptible to BSA binding compared with that of the linear long-chain PFOA. In contrast to the significant effects of strong BSA-PFOA interaction, the weak affinity of BSA-GenX binding did not influence the structure of protein and the cytotoxicity of GenX. The detailed characterization and direct comparisons of serum albumin interaction with new generation short-chain GenX will provide a better understanding for the toxicological properties of this new alternative.

Snapshot Survey of the Presence of Perfluoroalkyl Substances in Products, Articles, and the Environment in Ecuador

The Stockholm Convention on Persistent Organic Pollutants (POPs) is a legally binding instrument for 186 Parties (status: April 2023). Accordingly, among other responsibilities, countries are obliged to report the production, import, or export of the POPs listed in Annexes A, B, or C; provide information to registers; maintain inventories; and monitor the presence of POPs in the environment. In the broader context of international chemicals and waste management, producer responsibilities, harmonized reporting, and compliance with national and international regulations, Ecuador has addressed the newly listed group of perfluorinated alkyl substances (PFAS) in its national implementation plan and sent selected products from its national market for PFAS analysis. The products analyzed came from the initially listed fields of specific exemptions and acceptable purposes, including: fire-fighting foams; photographic aids; greasers/degreasers; various kinds of paper/packaging; textiles; and leather, coatings, cleaners, metal plating, and pesticides. Our results showed that the three PFAS presently listed in the Stockholm Convention could be quantified in only a few samples; additional PFAS, not yet listed in the Convention also had low detection frequencies. Although the number of samples was limited, the samples covered a large spectrum of sample matrices, making it possible to conclude that—once these products become waste and are regulated under the Basel Convention—they would not constitute a disposal problem. Nevertheless, verification of the presence of PFAS in products on the market is expected to pose an analytical challenge for both, developed and developing countries.

Impact of Environmental Exposures on Human Breast Milk Lipidome in Future Immune-Mediated Diseases.

The composition of human breast milk (HBM) exhibits significant variability both between individuals and within the same individual. While environmental factors are believed to play a role in this variation, their influence on breast milk composition remains inadequately understood. Herein, we investigate the impact of environmental factors on HBM lipid composition in a general population cohort. The study included mothers (All Babies In Southeast Sweden study) whose children later progressed to one or more immune-mediated diseases later in life: type 1 diabetes (n = 9), celiac disease (n = 24), juvenile idiopathic arthritis (n = 9), inflammatory bowel disease (n = 7), hypothyroidism (n = 6), and matched controls (n = 173). Lipidome of HBM was characterized by liquid chromatography combined with high-resolution mass spectrometry. We observed that maternal age, body mass index, diet, and exposure to perfluorinated alkyl substances (PFASs) had a marked impact on breast milk lipidome, with larger changes observed in the milk of those mothers whose children later developed autoimmune diseases. We also observed differences in breast milk lipid composition in those mothers whose offspring later developed autoimmune diseases. Our study suggests that breast milk lipid composition is modified by a complex interaction between genetic and environmental factors, and, importantly, this impact was significantly more pronounced in those mothers whose offspring later developed autoimmune/inflammatory diseases. Our findings also suggest that merely assessing PFAS concentration may not capture the full extent of the impact of chemical exposures; thus, the more comprehensive exposome approach is essential for accurately assessing the impact of PFAS exposure on HBM and, consequently, on the health outcomes of the offspring.

Passive Sampler Derived Profiles and Mass Flows of Perfluorinated Alkyl Substances (PFASs) across the Fram Strait in the North Atlantic.

Per- and polyfluorinated alkyl substances (PFAS) are a family of pollutants of high concern due to their ubiquity and negative human health impacts. The long-range marine transport of PFAS was observed during year-long deployments of passive tube samplers in the Fram Strait across three depth transects. Time weighted average concentrations ranged from 2.4-360 pg L-1, and 10 different PFAS were regularly observed. PFAS profiles and concentrations were generally similar to those previously characterized for polycyclic aromatic hydrocarbons (PAHs) at these sites. The detection of several anionic PFAS in "old" water demonstrated that they are not perfect water mass tracers, but are also transported to depth via settling particles. Mass flows of PFAS through the Fram Strait in and out of the Arctic Ocean were basically similar (112 ±82 Mg year-1 northward flow, 100 ±54 Mg year-1 southward flow). For FOSA, export from the Arctic Ocean via the Fram Strait exceeded import by Atlantic Water, likely due to preferential transport and deposition in the Arctic Ocean. These observations suggest PFAS in the Arctic are governed by the feedback loop previously described for PAHs in the region - with additional atmospheric transport delivering volatile PFAS to the Arctic, which then get exported further.

The role of helicity in PFAS resistance to degradation: DFT simulation of electron capture and defluorination.

Defluorination of perfluorinated alkyl substances (PFASs) via the direct capture of excess electrons poses a promising path to environmental decontamination. Herein we show that quantum-chemical model optimization methods can be adapted to simulate the changes to molecular geometry that result from electron capture. These reaction pathways demonstrate that the introduction of an additional electron causes a loss of the helical arrangement along linear carbon tail chains. Regaining helicity is sufficiently favourable to enable fluoride release in C7-C10 PFAS chains; shorter chains are enthalpically hindered from degradation while the additional charge is stabilized on longer chains by the greater entropy their flexibility permits. These results suggest that reductive PFAS treatment processes could be made more effective under high pressure or confined conditions.

Removal of PFAS from water by aquatic plants

We have found that aquatic plants can reduce the content of perfluorinated alkyl substances (PFAS) within a short period of time. The aim of this study was to determine the variation in the uptake of PFAS from contaminated water by various wetland plant species, investigate the effect of biomass on PFAS removal, and determine whether laccases and peroxidases are involved in the removal and degradation of PFAS. Seventeen emergent and one submerged wetland plant species were screened for PFAS uptake from highly contaminated lake water. The screening showed that Eriophorum angustifolium, Carex rostrata, and Elodea canadensis accumulated the highest levels of all PFAS. These species were thereafter used to investigate the effect of biomass on PFAS removal from water and for the enzyme studies. The results showed that the greater the biomass per volume, the greater the PFAS removal effect. The plant-based removal of PFAS from water is mainly due to plant absorption, although degradation also occurs. In the beginning, most of the PFAS accumulated in the roots; over time, more was translocated to the shoots, resulting in a higher concentration in the shoots than in the roots. Most PFAS degradation occurred in the water; the metabolites were thereafter taken up by the plants and were accumulated in the roots and shoots. Both peroxidases and laccases were able to degrade PFAS. We conclude that wetland plants can be used for the purification of PFAS-contaminated water. For effective purification, a high biomass per volume of water is required.

Food, nutrition, and fertility: from soil to fork

Food and nutrition-related factors, including foods and nutrients consumed, dietary patterns, use of dietary supplements, adiposity, and exposure to food-related environmental contaminants, have the potential to impact semen quality and male and female fertility; obstetric, fetal, and birth outcomes; and the health of future generations, but gaps in evidence remain. On 9 November 2022, Tufts University’s Friedman School of Nutrition Science and Policy and the school's Food and Nutrition Innovation Institute hosted a 1-d meeting to explore the evidence and evidence gaps regarding the relationships between food, nutrition, and fertility. Topics addressed included male fertility, female fertility and gestation, and intergenerational effects. This meeting report summarizes the presentations and deliberations from the meeting.Regarding male fertility, a positive association exists with a healthy dietary pattern, with high-quality evidence for semen quality and lower quality evidence for clinical outcomes. Folic acid and zinc supplementation have been found to not impact male fertility. In females, body weight status and other nutrition-related factors are linked to nearly half of all ovulation disorders, a leading cause of female infertility. Females with obesity have worse fertility treatment, pregnancy-related, and birth outcomes. Environmental contaminants found in food, water, or its packaging, including lead, perfluorinated alkyl substances, phthalates, and phenols, adversely impact female reproductive outcomes. Epigenetic research has found that maternal and paternal dietary-related factors can impact outcomes for future generations.Priority evidence gaps identified by meeting participants relate to the effects of nutrition and dietary patterns on fertility, gaps in communication regarding fertility optimization through changes in nutritional and environmental exposures, and interventions impacting germ cell mechanisms through dietary effects. Participants developed research proposals to address the priority evidence gaps. The workshop findings serve as a foundation for future prioritization of scientific research to address evidence gaps related to food, nutrition, and fertility.

Fluoropolymer Nanoparticles Synthesized via Reversible-Deactivation Radical Polymerizations and Their Applications.

Fluorinated polymeric nanoparticles (FPNPs) combine unique properties of fluorocarbon and polymeric nanoparticles, which has stimulated massive interest for decades. However, fluoropolymers are not readily available from nature, resulting in synthetic developments to obtain FPNPs via free radical polymerizations. Recently, while increasing cutting-edge directions demand tailored FPNPs, such materials have been difficult to access via conventional approaches. Reversible-deactivation radical polymerizations (RDRPs) are powerful methods to afford well-defined polymers. Researchers have applied RDRPs to the fabrication of FPNPs, enabling the construction of particles with improved complexity in terms of structure, composition, morphology, and functionality. Related examples can be classified into three categories. First, well-defined fluoropolymers synthesized via RDRPs have been utilized as precursors to form FPNPs through self-folding and solution self-assembly. Second, thermally and photoinitiated RDRPs have been explored to realize in situ preparations of FPNPs with varied morphologies via polymerization-induced self-assembly and cross-linking copolymerization. Third, grafting from inorganic nanoparticles has been investigated based on RDRPs. Importantly, those advancements have promoted studies toward promising applications, including magnetic resonance imaging, biomedical delivery, energy storage, adsorption of perfluorinated alkyl substances, photosensitizers, and so on. This Review should present useful knowledge to researchers in polymer science and nanomaterials and inspire innovative ideas for the synthesis and applications of FPNPs.

Untargeted Screening of Per- and Polyfluoroalkyl Substances (PFASs) in Airborne Particulate of Three Italian E-Waste Recycling Facilities

Poly- and perfluorinated alkyl substances (PFASs) are widely used in the electrical and electronic appliance industry to the point that waste of electrical and electronic equipment (WEEE), also known as e-waste, creates significant potential for PFAS exposure (by inhalation, ingestion, or dermal exposure) for people handling and recycling e-waste. The aim of this work was the development of an untargeted analytical approach in order to detect the presence of possible unknown PFASs in particulate matter collected in three Italian e-waste facilities through liquid chromatography coupled to high-resolution tandem mass spectrometry (LC-HR-MS/MS) in negative ionization mode. By means of three acquisition experiments, nine compounds were detected as candidate PFASs, and three were definitively confirmed by comparison with their authentic standards. Among these, bistriflimide (bis (trifluoromethylsulfonyl) imide), an ionic liquid with several promising technological applications, was the most abundant compound detected in all three recycling plants. This is the first study associating the presence of fluorinated ionic liquids with e-waste, and as these chemicals are not only toxic and persistent but also highly mobile, our results indicate the need to include them in future PFAS research. Only further data on their actual environmental diffusion will determine whether they are emerging pollutants or not.

Gestational hypertension, preeclampsia, and gestational diabetes mellitus after high exposure to perfluoroalkyl substances from drinking water in Ronneby, Sweden

BackgroundLeakage of fire-fighting foam from an airfield caused contamination of the drinking water supplied to a third of the population in Ronneby, resulting in very high serum levels of predominantly perfluorooctane sulfonate (PFOS) and perfluorohexane sulfonate (PFHxS). The results of studies investigating the association between exposure to perfluorinated alkyl substances (PFAS) and pregnancy complications are inconsistent, and studies at high exposures of PFOS and PFHxS are lacking. ObjectivesTo investigate the association between exposure to high levels of PFAS and gestational hypertension and preeclampsia, and gestational diabetes mellitus. MethodsWe retrieved data on 27 292 childbirths between 1995 and 2013 from the National Medical Birth Register for women that had a residential address in Blekinge county for at least one year before delivery. Residential history was used as a proxy for exposure by categorizing women into high-, intermediate-, or background exposed based on their residential address during the five-year period before childbirth. Data on confounders were retrieved from administrative registers. The outcomes were defined based on International Classification of Diseases codes. We used logistic regression to estimate odds ratios (OR) for gestational hypertension and preeclampsia, and gestational diabetes mellitus. We also investigated effect modification by fetal sex. ResultsWe found no evidence of increased risk of gestational hypertension and preeclampsia (OR 0.80; CI 0.63–1.03), nor gestational diabetes (OR 1.03; CI 0.67–1.58) after high PFAS exposure. There was no effect modification by fetal sex. DiscussionThis was the first study to investigate the association between high exposure to PFOS and PFHxS and pregnancy complications. The results from this study add important knowledge to public health management as new hotspots with high levels of PFAS are continuously discovered.

Comparison of the photocatalytic degradability of PFOA, PFOS and GenX using Fe-zeolite in water

Knowledge on the photocatalytic degradability of the emerging poly- and perfluorinated alkyl substances (PFAS) in water, specifically GenX, is limited. GenX has been detected globally in river water and is considered potentially more toxic than legacy PFAS. In this study, we compared the photocatalytic degradability of GenX with the legacy compounds perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) using Fe-zeolite photocatalysts. After 7 h of irradiation, GenX showed lower removal (79%) and defluorination (33%) as compared to PFOA (100% removal and 69% defluorination) and PFOS (100% removal and 51% defluorination). The quasi-first-order degradation rate of GenX (1.5 h1) was 12 and 1.2 times lower than PFOA (18.4 h−1) and PFOS (1.8 h−1), respectively. Additionally, PFOA's defluorination rate (0.9 h−1) was approximately 2.6 and 9 times higher than GenX (0.35 h−1) and PFOS (0.1 h−1), respectively. These outcomes correlate with GenX's lower hydrophobicity, leading to reduced adsorption (40%) compared to PFOA (99%) and PFOS (87%). Based on identified transformation products, we proposed a GenX degradation pathway, resulting in ultra-short-chain PFASs with a chain length of 2 and 3 carbon atoms, while PFOA and PFOS degraded stepwise, losing 1 carbon-fluorine bond at a time, leading to gradually shorter chain lengths (from 7 to 2 carbon atoms). In conclusion, GenX is more challenging to remove and degrade due to its lower adsorption on the photocatalyst, potential steric hindrance, and higher production of persistent ultra-short-chain transformation products through photocatalysis.

Rapid PFOS mineralization with peroxydisulfate activation process mediated by N modified Fe-based catalyst

As the cheap and efficient catalysts, the iron-based catalysts have been considered as one of the most promising catalysts for peroxydisulfate (PDS) activation and the development of high-performance iron-based catalysts are attracting growing attentions. In this work, a magnetic Fe-based catalysts (Fe/NC-1000) was obtained by using Fe modified ZIF-8 as the precursor and used to activate the PDS for the degradation of perfluorooctane sulphonate (PFOS). Morphology and structure analysis showed that the resulted Fe/NC-1000 catalyst was displayed porous spheres (40–60 nm) and mainly composed of Fe0, FeNx and carbon. When Fe/NC-1000 was employed to activate the PDS (0.1 g/L of catalyst dosage, 0.5 g/L of PDS dosage and at initial pH of 4.6), the Fe/NC-1000/PDS system exhibited excellent efficiency (97.9 ± 0.1) % for PFOS (10 mg/L) degradation within 30 min. The quenching tests and EPR results revealed that the Fe/NC-1000/PDS system degraded PFOS primarily through singlet oxygen (1O2) evolution and electron-transfer process. Besides, based on the degradation byproducts determined by LC-MS-MS, the PFOS first occurred de-sulfonation to form PFOA, and then the resulted PFOA underwent stepwise defluorination in the Fe/NC-1000/PDS system. Density Functional Theory (DFT) calculations and electrochemistry tests strongly confirmed that Fe/NC-1000 exhibited high electron transfer efficiency, resulting in promoted performance on activating PDS. Importantly, the results of Ecological Structure-Activity Relationship (ECOSAR) analysis showed that the intermediates were lowly toxic during the PFOS degradation, manifesting a green process for PFOS removal. This study would provide more understandings for the persulfate activation process mediated by Fe-based catalysts for Perfluorinated alkyl substances (PFAS) elimination.

Early detection of emerging persistent perfluorinated alkyl substances (PFAS) along the east coast of India

Perfluorooctanoic acid (PFOA) and Perfluorooctane sulfonate (PFOS) are resistant to breakdown and are now considered global contaminants. However, interest in these recalcitrant compounds among scientists and legislators has grown significantly in recent years. In the present study, we analyzed the level of PFOA and PFOS contamination in surface water from the coastal regions of Tamil Nadu and West Bengal. After solid phase extraction, 49 samples were analyzed by liquid chromatography coupled with mass spectrometry (LOD ≤ 1.5 ng L−1). The PFOA and PFOS present in all samples at the highest concentration were found in the Ennore coastal region (reaching a maximum of 24.8 ng L−1 and 13.9 ng L−1 in CH-6 and CH-14 respectively). Similarly, on the West Bengal coast, concentrations of PFOA ranged from <1.5 to 14.0 ng L−1 and <1.3 to 8.2 ng g−1 in water and sediment respectively. PFOS concentrations in water and sediment ranged from <1.2 to 9.0 ng L−1 and <1.2 to 7.9 ng g−1, respectively. According to the principal component analysis, the majority of the variances (65.04 %) show a positive association, which points to industrial and domestic discharges as significant point sources of these compounds. The results from this study could be used to determine and understand the levels of PFOA and PFOS contamination along the Indian Coast as well as provide baseline information for imminent monitoring investigations. The environmental occurrences of PFOA and PFOS reported in the current study would allow policymakers to take appropriate measures to safeguard coastal ecosystems or reduce the likelihood of contamination, creating a sustainable and healthy environment.

Selective Detection and Identification of Perfluorinated Alkyl Substances Using Low-Resolution Precursor Ion Mass Spectrometry

Selective Detection and Identification of Perfluorinated Alkyl Substances Using Low-Resolution Precursor Ion Mass Spectrometry

Persistent organic pollutants associate with liver disease in a Finnish general population sample.

Persistent organic pollutants (POPs) have multiple adverse effects on human health. Recent studies show a possible association with liver disease, but population-based data are scarce. In this population-based study, we studied the associations between POPs and biomarkers of liver disease and incident liver disease. This study consisted of 2789 adults that participated in the environmental toxin subset of the Finnish health-examination survey, FINRISK 2007. Toxins were measured from serum samples, and standard liver tests and dynamic aspartate aminotransferase-alanine aminotransferase ratio (dAAR) were measured as biomarkers of liver function. Associations between POPs and the biomarkers were then analysed using linear regression. Associations between POPs and incident liver disease (n = 36) were analysed by Cox regression. Organochlorine pesticides (OCPs), polychlorinated biphenyls (PCBs) and several perfluorinated alkyl substances exhibited statistically significant positive associations with several biomarkers of liver injury (betacoefficient per SD 0.04-0.14, p < 0.05). These associations were stronger in subgroups of individuals with obesity or non-alcoholic fatty liver disease. OCPs, PCBs and perfluoro-octanoic acid also had significant positive associations with dAAR, which can be used to predict risk of incident severe liver outcomes (beta coefficient per SD 0.05-0.08, p < 0.05). OCPs and PCBs were also significantly and positively associated with incident liver disease (hazard ratio per SD 1.82 95% CI 1.21-2.73, p < 0.01 and hazard ratio per SD 1.69, 95% CI 1.07-2.68, p < 0.05 respectively). Several POPs show positive associations with markers of liver injury and incident liver disease, suggesting that environmental toxins are important risk factors for chronic liver disease.

Degradation of Perfluorooctanoic Acid by Chlorine Radical Triggered Electrochemical Oxidation System.

Electrochemical oxidation (EO) has been shown to have the unique ability to degrade perfluorooctanoic acid (PFOA), although the radical chemistry involved in this degradation is unclear, particularly in the presence of chloride ions (Cl-). In this study, reaction kinetics, free radical quenching, electron spin resonance, and radical probes were used to examine the roles of ·OH and reactive chlorine species (RCS, including Cl·, Cl2•-, and ClO·) in the EO of PFOA. Using EO in the presence of NaCl, PFOA degradation rates of 89.4%-94.9% and defluorination rates of 38.7%-44.1% were achieved after 480 min with PFOA concentrations ranging from 2.4 to 240 μM. The degradation occurred via the synergistic effect of ·OH and Cl· rather than through direct anodic oxidation. The degradation products and density functional theory (DFT) calculations revealed that Cl· triggered the first step of the reaction, thus the initial direct electron transfer was not the rate-limiting step of PFOA degradation. The change in Gibbs free energy of the reaction caused by Cl· was 65.57 kJ mol-1, which was more than two times lower than that triggered by ·OH. However, ·OH was involved in the subsequent degradation of PFOA. The synergistic effect of Cl· and ·OH in PFOA degradation is demonstrated for the first time in this study, which is promising for the development of electrochemical technology to remove perfluorinated alkyl substances from the environment.

Prenatal exposure to persistent organic pollutants and molar-incisor hypomineralization among 12-year-old children in the French mother-child cohort PELAGIE

BackgroundExceptional episodes of exposure to high levels of persistent organic pollutants have already been associated with developmental defects of enamel among children, but knowledge is still scarce concerning the contribution of background levels of environmental contamination. MethodsChildren of the French PELAGIE mother-child cohort were followed from birth, with collection of medical data and cord blood samples that were used to measure polychlorinated biphenyls (PCBs), organochlorine pesticides (OCs), and perfluorinated alkyl substances (PFASs). At 12 years of age, molar-incisor hypomineralization (MIH) and other enamel defects (EDs) were recorded for 498 children. Associations were studied using logistic regression models adjusted for potential prenatal confounders. ResultsAn increasing log-concentration of β-HCH was associated with a reduced risk of MIH and EDs (OR = 0.55; 95% CI, 0.32–0.95, and OR = 0.65; 95% CI, 0.43–0.98, respectively). Among girls, intermediate levels of p,p’-DDE were associated with a reduced risk of MIH. Among boys, we observed an increased risk of EDs in association with intermediate levels of PCB 138, PCB 153, PCB 187, and an increased risk of MIH with intermediate levels of PFOA and PFOS. ConclusionsTwo OCs were associated with a reduced risk of dental defects, whereas the associations between PCBs and PFASs and EDs or MIH were generally close to null or sex-specific, with an increased risk of dental defects in boys. These results suggest that POPs could impact amelogenesis. Replication of this study is required and the possible underlying mechanisms need to be explored.

Unwanted Ingredients—Highly Specific and Sensitive Method for the Extraction and Quantification of PFAS in Everyday Foods

Perfluorinated alkyl substances (PFAS) are anthropogenic substances and can only come from polluted sources. There are many classes of PFAS which can be transformed to perfluoalkyl carboxylic acids and perfluoroalkyl sulfonic acids in the environment. Once they are in this form, they are environmentally mobile and extremely stable with half-lives of decades. These compounds are not innocuous and are implicated in causing many different diseases. In this publication, a method for the extraction and quantitation of perflurocarboxylic acids and perfluorosulfonic acids, using high-resolution liquid chromatography mass spectrometry (HRMS), is evaluated. A QuEChERS extraction method was performed on tomatoes, strawberries and milk purchased from different supermarkets on different days. Recoveries from milk and tomatoes were between 80 and 120%. Matrix effects were significant for strawberries and tomatoes and stable isotope internal standards were required to compensate. PFBA was found in all 3 food types. The total PFAS was 0.68 ng g−1 in milk, 0.20 ng g−1 in strawberries and 0.36 ng g−1 in tomatoes. This study demonstrates the importance of using a robust analytical method to investigate the PFAS content of complex food matrices and in particular the contribution of short-chain PFAS to overall dietary consumption.

1 H-Nuclear Magnetic Resonance Metabolomics Analysis of Arabidopsis thaliana Exposed to Perfluorooctanoic Acid and Perfluoroctanesulfonic Acid.

Perfluorinated alkyl substances (PFAS) are ubiquitous environmental contaminants that are widely used in consumer products and fire suppression foams. The presence of PFAS in ground and surface water can create a route for PFAS to enter the soil, exposing ecosystems (including agroecosystems), where they will move through the food web via biomagnification. The toxicity of PFAS to plants, particularly in agricultural ecosystems, is of emerging concern due to the application of biosolids that are often contaminated with PFAS. Nevertheless, due to the low concentrations of PFAS in most agricultural soils, the direct impact of PFAS on plant health is not well understood. We used 1 H-nuclear magnetic resonance (NMR) metabolomics to explore the effects of exposure of two key PFAS, perfluorooctanoic acid and perfluorooctanesulfonic acid, on Arabidopsis thaliana, a model organism. We found that Arabidopsis exhibited an accumulation of multiple metabolites, including soluble sugars (glucose and sucrose), multiple amino acids, and tri-carboxylic acid (TCA) cycle intermediates, suggesting that PFAS exposure impacts the metabolism of plants by causing an accumulation of stress-related amino acids and soluble sugars that drives increased activity of the TCA cycle. The present study shows that 1 H-NMR metabolomics is a viable tool for investigating changes in the metabolic profile of plants exposed to PFAS and can be used to illuminate the stress response of plants in a high-throughput, nonbiased manner. Environ Toxicol Chem 2023;42:663-672. © 2022 SETAC.