[Determination of 13 perfluorinated and polyfluoroalkyl substances in fishes by QuEChERS-ultra-high performance liquid chromatography-tandem mass spectrometry].

Perfluorinated and polyfluoroalkyl substances (PFASs) are compounds characterized by at least one perfluorinated carbon atom in an alkyl chain linked to side-chain groups. Owing to their unique chemical properties, these compounds are widely used in industrial production and daily life. However, owing to anthropogenic activities, sewage discharge, surface runoff, and atmospheric deposition, PFASs have gradually infiltrated the environment and aquatic resources. With their gradual accumulation in environmental waters, PFASs have been detected in fishes and several fish-feeding species, suggesting that they are bioconcentrated and even amplified in aquatic organisms. PFASs exhibit high intestinal absorption efficiencies, and they bioaccumulate at higher trophic levels in the food chain. They can be bioconcentrated in the human body via food (e. g., fish) and thus threaten human health. Therefore, establishing an efficient analytical technique for use in analyzing PFASs in typical fish samples and providing technical support for the safety regulation and risk assessment of fish products is necessary. In this study, by combining solvent extraction and magnetic dispersion-solid phase extraction (d-SPE), an improved QuEChERS method with ultra-high performance liquid chromatography-tandem mass spectrometry (UHPLC-MS/MS) was developed for the determination of 13 PFASs in fish samples. Fe3O4-TiO2 can be used as an ideal adsorbent in the removal of sample matrix interference and a separation medium for the rapid encapsulation of other solids to be isolated from the solution. Based on the matrix characteristics of the fish products and structural properties of the target PFASs, Fe3O4-TiO2 and N-propyl ethylenediamine (PSA) were employed as adsorbents in dispersive purification. The internal standard method was used in the quantitative analyses of the PFASs. To optimize the sample pretreatment conditions of analyzing PFASs, the selection of the extraction solvent and amounts of Fe3O4-TiO2 and PSA were optimized. Several PFASs contain acidic groups that are non-dissociated in acidic environments, thus favoring their entry into the organic phase. In addition, acidified acetonitrile can denature and precipitate the proteins within the sample matrix, facilitating their removal. Finally, 2% formic acid acetonitrile was used as the extraction solvent, and 20 mg Fe3O4-TiO2, 20 mg PSA and 120 mg anhydrous MgSO4 were used as purification adsorbents. Under the optimized conditions, the developed method exhibited an excellent linearity (R≥0.9973) in the range of 0.01-50 µg/L, and the limits of detection (LODs) and quantification (LOQs) ranged from 0.001-0.023 and 0.003-0.078 µg/L, respectively. The recoveries of the 13 PFASs at low, medium, and high spiked levels (0.5, 10, and 100 µg/kg) were 78.1%-118%, with the intra- and inter-day precisions of 0.2%-11.1% and 0.8%-8.7%, respectively. This method was applied in analyzing real samples, and PFASs including perfluorooctanesulfonic acid, perfluorooctanoic acid, perfluoroundecanoic acid, perfluorododecanoic acid, and perfluorotridecanoic acid, were detected in all 11 samples evaluated. This method is simple, sensitive, and suitable for use in analyzing PFASs in fish samples.

[Risk appraisal of dietary intake of per- and polyfluoroalkyl substances by the Veneto population living in the area with water contamination. Update based on EFSA 2020 limits. Food surveillance campaign 2016-2017]. / Valutazione del rischio legato all'assunzione di sostanze per- e polifluoroalchiliche per via alimentare da parte della popolazione veneta residente nella zona con contaminazione delle acque. Aggiornamento sulla base dei limiti EFSA 2020. Campagna di so.

The Veneto Region (Northern Italy) conducted a monitoring campaign in the years 2016-2017 in order to evaluate the concentration of per- and polyfluoroalkyl substances (PFASs) in foods in the area affected by the water contamination discovered in 2013. The risk assessment for the resident population was conducted by the Italian National Institute of Health (ISS) in 2018 and updated in 2021. The European Food Safety Agency (EFSA) updated the limits used by ISS, in particular adding a limit for the sum of four PFAS molecules in 2020. In this work, the risk assessment conducted by ISS is reviewed in light of the new limit of 4.4 ng/kg body weight for the sum of perfluorooctanoic acid (PFOA), perfluorooctanesulfonic acid (PFOS), perfluorononanoic acid (PFNA), and perfluorohexanesulfonate (PFHxS). In the adult population (18-65 years), total weekly intakes, calculated for the years preceding 2013, resulted more than ten times the EFSA 2020 limit, more than five times in the intermediate period 2013-2017 - preceding the implementation of mitigation actions through double filtration of the water of the aqueduct -, by more than three times in the period after 2018, and yet by almost seven times for those who supply contaminated groundwater through private wells. The food contribution for those who use filtered water from the aqueduct is equal to 20% of the total weekly income.

Occurrence and potential ecological risks of PFAS in Pampulha Lake, Brazil, a UNESCO world heritage site.

Per- and polyfluoroalkyl substances (PFAS) comprise >4000 synthetic substances used in industrial applications and consumer products. PFAS used daily in households and manufacturing plants end up in domestic sewage, and industrial effluents can be discharged to surface water. Urban watersheds located in low and middle-income countries (LMIC), which lack sanitation infrastructure, are potential recipients of waste containing PFAS. Yet, only a few studies report PFAS occurrence in urban reservoirs and lakes, especially those located in the Global South due to resource limitations. This is the first study aimed to assess PFAS occurrence and ecological risks in Pampulha Lake, Brazil, a site which represents the reality of many other urban watersheds in LMIC as it is surrounded by densely populated areas and manufacturing plants. Surface water samples were collected monthly for 1 year from four sampling points at Pampulha Lake. Sample analysis was based on US Environmental Protection Agency Method 1633, which employs solid phase extraction followed by liquid chromatography coupled to tandem mass spectrometry (LC-MS/MS). Species sensitivity distribution (SSD) curves were built to identify potentially susceptible species based on detected water concentrations. Bioaccumulation was estimated for fish tissue. Short-chain (perfluorobutanesulfonic acid, PFBS and perfluorohexanoic acid, PFHxA) and long-chain PFAS (perfluorodecanoic acid, PFDA; perfluorooctanoic acid, PFOA; perfluorododecanoic acid, PFDoA; and perfluorooctanesulfonic acid, PFOS) were detected at the µg L-1 range. Total PFAS concentrations in the wet season were generally higher than in the dry season, likely due to limited capacity of the treatment plant processing water from tributaries which receive raw sewage. More than 5 % of aquatic species are potentially susceptible to chronic effects of PFOS at detected concentrations (0.2-2.2 µg L-1). Predicted bioaccumulation of PFOS in fish was above advisory diet intake levels for humans. Results emphasize the need for studies related to PFAS occurrence in watersheds located in LMIC.

A multi-platform approach for the comprehensive analysis of per- and polyfluoroalkyl substances (PFAS) and fluorine mass balance in commercial ski wax products.

The unique properties of per- and polyfluoroalkyl substances (PFAS) have led to their extensive use in consumer products, including ski wax. Based on the risks associated with PFAS, and to align with PFAS regulations, the international ski federation (FIS) implemented a ban on products containing "C8 fluorocarbons/perfluorooctanoate (PFOA)" at all FIS events from the 2021/2022 season, leading manufactures to shift their formulations towards short-chain PFAS chemistries. To date, most studies characterising PFAS in ski waxes have measured a suite of individual substances using targeted analytical approaches. However, the fraction of total fluorine (TF) in the wax accounted for by these substances remains unclear. In this study, we sought to address this question by applying a multi-platform, fluorine mass balance approach to a total of 10 commercially available ski wax products. Analysis of TF by combustion ion chromatography (CIC) revealed concentrations of 1040-51700 µg F g-1 for the different fluorinated waxes. In comparison, extractable organic fluorine (EOF) determined in methanol extracts by CIC (and later confirmed by inductively-coupled plasma-mass spectrometry and 19F- nuclear magnetic resonance spectroscopy) ranged from 92 to 3160 µg g-1, accounting for only 3-8.8 % of total fluorine (TF). Further characterisation of extracts by cyclic ion mobility-mass spectrometry (IMS) revealed 15 individual PFAS with perfluoroalkyl carboxylic acid concentrations up to 33 µg F g-1, and 3 products exceeding the regulatory limit for PFOA (0.025 µg g-1) by a factor of up to 100. The sum of all PFAS accounted for only 0.01-1.0 % of EOF, implying a high percentage of unidentified PFAS, thus, pyrolysis gas chromatography-mass spectrometry was used to provide evidence of the nature of the non-extractable fluorine present in the ski wax products.

Occurrence of a "forever chemical" in the atmosphere above pristine Amazon Forest.

Per- and polyfluoroalkyl substances (PFAS), often referred to as "forever chemicals", are a class of man-made, extremely stable chemicals, which are widely used in industrial and commercial applications. Exposure to some PFAS is now known to be detrimental to human health. By virtue of PFAS long residence times, they are widely detected in the environment, including remote locations such as the Arctics, where the origin of the PFAS is poorly understood. It has been suggested that PFAS may be transported through contaminated waters, leading to accumulation in coastal areas, where they can be aerosolised via sea spray, thereby extending their geographical distribution far beyond their original source regions. The aim of this work is to investigate, for the first time, whether "forever chemicals" could be transported to areas considered to be pristine, far from coastal sites. This study was performed at the Amazonian Tall Tower Observatory (ATTO), a unique remote site situated in the middle of the Amazon rainforest, where a restricted PFAS, perfluorooctanoic acid (PFOA), was observed with concentrations reaching up to 2 pg/m3. A clear trend of increasing concentration with sampling height was observed and air masses from the south over Manaus had the highest concentrations. Atmospheric lifetime estimations, removal mechanisms supported by measurements at two heights (320 and 42 m above the rainforest), and concentration spikes indicated a long-range transport of PFOA to pristine Amazon rainforest. Potential sources, including industrial activities in urban areas, were explored, and historical fire management practices considered. This research presents the first measurements of PFAS in the atmosphere of Amazon rainforest. Remarkably, even in this remote natural environment, appreciable levels of PFAS can be detected. This study provides valuable insights into the long-range transport of the anthropogenic "forever chemical" into a remote natural ecosystem and should raise awareness of potential environmental implications.

Carry-over rate of per- and polyfluoroalkyl substances to raw milk and human exposure risks in different regions of China.

The widespread presence of per- and polyfluoroalkyl substances (PFAS) in various environmental matrices and their adverse health effects have gained worldwide attention. Therefore, numerous studies have focused on human exposure to PFAS through different pathways, such as fish and drinking water, and little attention has been paid to milk consumption. This study aimed to explore the transfer of PFAS by investigating the occurrence of PFAS in cow feed, drinking water, and raw milk from 20 regions of China and to assess the risk of human exposure to PFAS from raw milk. In total, 13, 15, and 7 PFAS were detected in cow feed, drinking water, and raw milk with total concentrations (∑PFAS) of 5.59 ± 2.91 ng/g (mean ± standard deviation), 11.91 ± 23.12 ng/L, and 0.15 ± 0.13 ng/mL, respectively. Perfluoropentanoic acid (PFPeA) was dominant with a concentration of 2.28 ± 1.75 ng/g, approximately 40.7 % of ∑PFAS in feed. Perfluorooctanoic acid (PFOA) and perfluorobutanoic acid (PFBA) were the dominant compounds found in drinking water at 4.80 ± 14.37 and 3.01 ± 6.06 ng/L, respectively. Additionally, PFOA (0.08 ± 0.09 ng/mL) was the most significant compound in raw milk, contributing 51.5 % of ∑PFAS. Moreover, the results of the carry-over rate (COR) were as follows: perfluorooctanesulfonic acid (PFOS, 29.58 %) > PFOA (15.78 %) > perfluorobutanesulfonic acid (PFBS, 9.45 %). According to the reference dose (RfD) established by the European Food Safety Authority (EFSA) in 2018, there is a potential toxicological hazard of PFOA exposure for preschool children through milk consumption. Notably, the health risk from PFOS for 1-year-old children in Central China exceeded that observed for humans in other regions and age groups. Our results showed that PFOS and PFOA were more likely to accumulate in cows and to be constantly transferred to milk, thus increasing the human health risk, especially in children.

Mobilization of per- and poly-fluoroalkyl substances (PFAS) in soils with different organic matter contents.

There is considerable interest in addressing soils contaminated with per- and polyfluoroalkyl substances (PFAS) because of the PFAS in the environment and associated health risks. The neutralization of PFAS in situ is challenging. Consequently, mobilizing the PFAS from the contaminated soils into an aqueous solution for subsequent handling has been pursued. Nonetheless, the efficiency of mobilization methods for removing PFAS can vary depending on site-specific factors, including the types and concentrations of PFAS compounds, soil characteristics. In the present study, the removal of perfluorooctanoate (PFOA) and perfluorooctane sulfonate (PFOS) from artificially contaminated soils was investigated in a 2D laboratory setup using electrokinetic (EK) remediation and hydraulic flushing by applying a hydraulic gradient (HG) for a duration of 15 days. The percent removal of PFOA by EK was consistent (∼80%) after a 15-day treatment for all soils. The removal efficiency of PFOS by EK significantly varied with the OM content, where the PFOS removal increased from 14% at 5% OM to 60% at 50% OM. With HG, the percent removal increased for both PFOA and PFOS from about 20% at 5% OM up to 80% at 75% OM. Based on the results, the mobilization of PFAS from organic soil would be appropriate using both hydraulic flushing and EK considering their applicability and advantages over each other for site-specific factors and requirements.

Perfluoroalkyl substances in the meat of Polish farm animals and game - Occurrence, profiles and dietary intake.

Meat from farm animals (pigs, cattle and poultry) and game (wild boar and deer) was analysed in terms of thirteen perfluoroalkyl substances (PFASs). Wild boar muscle tissue was statistically significantly more contaminated than muscle tissue from other animals, and the species order of the lower-bound (LB) sum of four (∑4) PFAS (perfluorooctanesulfonic acid (PFOS), perfluorooctanoic acid, perfluorononanoic acid and perfluorohexanesulfonic acid) concentrations was wild boar > cattle > deer > pigs > poultry. None of the samples exceeded the maximum levels set by Commission Regulation (EU) 2023/915. Linear PFOS was the most frequently detected compound (in 21 % of all samples analysed and 100 % of wild boar samples), reaching its highest concentration of 1.87 µg/kg wet weight in wild boar. Dietary intake was estimated on the basis of the average per-serving consumption of pork, beef and poultry, and in the absence of such data for game, a 100 g portion was used for the calculation. Mean LB∑4 PFAS concentrations led to intakes between 0.000 and 1.75 ng/kg body weight (BW) for children and 0.000 and 0.91 ng/kg BW for adults. The potential risk to consumers was assessed in relation to the tolerable weekly intake (TWI) of 4.4 ng/kg BW established by the European Food Safety Authority in 2020. Exposure associated with the consumption of poultry, pork, beef and venison was negligible, being only <1 % of the TWI for children and adults; higher exposure was found to associate with the consumption of wild boar, being 63 % and 21 % of the TWI for children and adults, respectively. The findings of this research suggest that the intake of PFASs through the consumption of meat from Polish livestock and deer is unlikely to be a health concern. However, frequent consumption of wild boar meat could be a significant source of PFASs.

A sensitive method for the determination of per- and polyfluoroalkyl substances in food and food contact material using high-performance liquid chromatography coupled with tandem mass spectrometry.

Dietary intake is the major pathway of human exposure to per- and polyfluoroalkyl substances (PFAS). Due to their generally very low concentrations in food, especially for foods of plant origin, and their toxicological relevance, demand is growing for improved selective and sensitive analytical methods for the determination of PFAS in the lower ng/kg range. The relevance is pointed out due to the fact that the European Commission has published limits of quantification (LOQs) in the lower ng/kg range for different food matrices in Recommendation (EU) 2022/1431 on the monitoring of perfluoroalkyl substances in food. For example, LOQs of 2 ng/kg for perfluorooctanesulfonic acid (PFOS), 1 ng/kg for perfluorooctanoic acid (PFOA), 1 ng/kg for perfluorononanoic acid (PFNA) and 4 ng/kg for perfluorohexanesulfonic acid (PFHxS) in fruit, vegetables and baby foods are required. A new, very sensitive method is presented here for the determination of 22 PFAS in food and food contact materials. The method is based on liquid-solid extraction and automated clean-up using two solid phase extraction techniques. The analytes are separated and detected by HPLC-MS/MS. A limit of detection (LOD) of 0.33 ng/kg and an LOQ of 1.0 ng/kg are attained for plant foods such as fruits and vegetables as well as for milk and baby food. For foods of animal origin such as egg, meat, fish and paper-based food contact materials an LOD of 1.6 ng/kg as well as an LOQ of 5.0 ng/kg are attained. PFOS and PFOA were the most abundant compounds in the food samples with concentration as high as 1,051 ng/kg of PFOA in sea weed samples and 772 ng/kg of PFOS in eggs samples. In food contact material samples, higher levels were found with a maximum of 310,000 ng/kg PFHxA. In sum the presented method firstly allows determination of PFAS in a wide variety of foodstuffs and paper-based food contact materials at EU-required concentration ranges.

Towards elevated perfluorooctanoic acid (PFOA) enrichment in water: Sequential liquid-liquid extraction pretreatment for ion chromatography detection.

The widespread detection of perfluorooctanoic acid (PFOA) in the environment has raised significant concerns. The standard PFOA analytical method relies on expensive solid-phase extraction (SPE) and liquid chromatography tandem mass spectrometry (LC-MS/MS) instruments, making routine use prohibitive. We herein proposed a cost-effective yet novel enrichment method for determining PFOA at ng L-1 level. This method entailed a two-step sample preparation process: firstly, PFOA was extracted and enriched using a forward-extraction under acidic conditions, followed by a backward-extraction and enrichment step utilizing alkaline water. The enriched samples were subsequently subjected to a common ion chromatography (IC). Results reveal that maintaining a forward-extraction pH below its pKa value (2.8) is essential, as protonated PFOA proves effective in enhancing the enrichment factor (EF). The challenge lied in driving PFOA from forward-extractant to aqueous backward-extractant due to the decreased hydrophobicity of deprotonated PFOA (log Kow2 = 1.0). In addition, we found that evaporating forward-extractant with alkaline backward-extractant (containing 5% methanol) reduced potential analytical uncertainties associated with PFOA evaporation and sorption. Under optimal conditions, the method achieved a detection limit of 9.2 ng L-1 and an impressive EF value of 719. Comparison with SPE-LC-MS/MS confirmed the proposed method as a promising alternative for PFOA determination. Although initially targeted for PFOA, the novel methodology is likely applicable to preconcentration of other poly-fluoroalkyl substances.

Evaluation and prediction of anthropogenic impacts on long-term multimedia fate and health risks of PFOS and PFOA in the Elbe River Basin.

Perfluorooctane sulfonic acid (PFOS) and perfluorooctanoic acid (PFOA) have aroused great concern owing to their widespread occurrence and toxic effects. However, their long-term trends and multimedia fate remain largely unknown. Here, we investigate the spatiotemporal characteristics and periodic oscillations of PFOS and PFOA in the Elbe River between 2010 and 2021. Anthropogenic emission inventories and multimedia fugacity model were developed to analyse their historical and future transport fates and quantify related human risks in each medium for the three age groups. The results show that average PFOS and PFOA concentrations in the Elbe River were 4.08 and 3.41 ng/L, declining at the annual rate of 7.36% and 4.98% during the study period, respectively. Periodic oscillations of their concentrations and mass fluxes were most pronounced at 40-60 and 20-40 months. The multimedia fugacity model revealed that higher concentrations occurred in fish (PFOS: 14.29, PFOA: 0.40 ng/g), while the soil was their dominant sink (PFOS: 179, PFOA: 95 tons). The exchange flux between water and sediment was the dominant pathway in multimedia transportation (397 kg/year). Although PFOS and PFOA concentrations are projected to decrease by 22.41% and 50.08%, respectively, from 2021 to 2050, the hazard quotient of PFOS in fish is a low hazard. This study provides information for the assessment of PFOS and PFOA pollution in global watersheds and the development of related mitigation policies, such as banning fish predation in polluted rivers, to mitigate their risks.

Molecularly imprinted resin modified with ionic liquid for dispersive filter extraction and determination of perfluoroalkyl acids in eggs.

Perfluoroalkyl acids (PFAAs) are emerging pollutants that endangers food safety. Developing methods for the selective determination of trace PFAAs in complex samples remains challenging. Herein, an ionic liquid modified porous imprinted phenolic resin-dispersive filter extraction-liquid chromatography-tandem mass spectrometry (IL-PIPR-DFE-LC-MS/MS) method was developed for the determination of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) in eggs. The new IL-PIPR adsorbent was prepared at room temperature, which avoids the disorder and instability of the template at high temperatures. The imprinting factor of IL-PIPR for PFOA and PFOS exceeded 7.3. DFE, combined with IL-PIPR (15 mg), was used to extract PFOA and PFOS from eggs within 15 min. The established method exhibits low limits of detection (0.01-0.02 ng/g) and high recoveries (84.7%-104.7%), which surpass those of previously reported methods. This work offers a new approach to explore advanced imprinted adsorbents for PFAAs, efficient sample pretreatment technique, and analytical method for pollutants in foods.

Per- and polyfluoroalkyl substances (PFASs) in bivalve molluscs from Shandong Province, China: Occurrence, distribution, and implications for human consumption.

We examined the occurrence and levels of 19 legacy and emerging per- and polyfluoroalkyl substances (PFASs) in 7 species of marine bivalve molluscs collected from four coastal cities of Shandong Province, China. Perfluorooctanoic acid (PFOA) was the most prevalent component, accounting for 68.1 % of total PFASs. The total PFASs in bivalve molluscs ranged from 0.86 to 6.55 ng/g wet weight, with the highest concentration found in Meretrix meretrix L. The concentration of total PFASs in bivalve molluscs showed the following trend: clams > scallops > oysters > mussels. Estimation on the human intake of PFASs from consumption of bivalve molluscs resulted in hazard ratios (HR) ranging from 0.12 to 6.40. Five of the seven species had HR >1, indicating high exposure risks associated with PFASs. Therefore, the occurrence of PFASs in marine biota is particularly concerning and further investigations on the sources of PFASs in Shandong are warranted.

Total and Class-Specific Determination of Fluorinated Compounds in Consumer and Food Packaging Samples Using Fluorine-19 Solid-State Nuclear Magnetic Resonance Spectroscopy.

Hamburger wrapping paper, coated with water-based barrier coatings, used in the food packaging industry was studied by using the total organic fluorine (TOF) method based on combustion ion chromatography and fluorine-19 solid-state nuclear magnetic resonance (19F ss-NMR) spectroscopy. Although the TOF method is a fast and affordable method used to screen for per- and polyfluoroalkyl substances (PFAS), the amount of fluorine it measures is heavily dependent on the extraction step and, therefore could lead to inaccurate results. Fluorine-19 ss-NMR spectroscopy can differentiate between organic and inorganic fluorinated sources, eliminating the need for sample clean up. To illustrate this, the 19F ss-NMR spectra of clean coated paper samples that contained naturally occurring F- ions from the talc raw material and spiked samples containing perfluorooctanoic acid were compared. A range of experimental conditions was explored to improve sensitivity for low PFAS concentrations (in the order of 10-20 mg/kg). Despite the disadvantages of ss-NMR spectroscopy, such as the low limit of detection and resolution, the results demonstrate it can be a viable tool to directly detect PFAS moieties in consumer and food packaging. Therefore, 19F solid-state NMR spectroscopy challenges and complements current methods, which only provide indirect evidence of the presence of PFAS.

Association of diet with per- and polyfluoroalkyl substances in plasma and human milk in the New Hampshire Birth Cohort Study.

Per- and polyfluoroalkyl substances (PFAS) are related to various adverse health outcomes, and food is a common source of PFAS exposure. Dietary sources of PFAS have not been adequately explored among U.S. pregnant individuals. We examined associations of dietary factors during pregnancy with PFAS concentrations in maternal plasma and human milk in the New Hampshire Birth Cohort Study. PFAS concentrations, including perfluorohexane sulfonate (PFHxS), perfluorooctane sulfonate (PFOS), perfluorooctanoate (PFOA), perfluorononanoate (PFNA), and perfluorodecanoate (PFDA), were measured in maternal plasma collected at ∼28 gestational weeks and human milk collected at ∼6 postpartum weeks. Sociodemographic, lifestyle and reproductive factors were collected from prenatal questionnaires and diet from food frequency questionnaires at ∼28 gestational weeks. We used adaptive elastic net (AENET) to identify important dietary variables for PFAS concentrations. We used multivariable linear regression to assess associations of dietary variables selected by AENET models with PFAS concentrations. Models were adjusted for sociodemographic, lifestyle, and reproductive factors, as well as gestational week of blood sample collection (plasma PFAS), postpartum week of milk sample collection (milk PFAS), and enrollment year. A higher intake of fish/seafood, eggs, coffee, or white rice during pregnancy was associated with higher plasma or milk PFAS concentrations. For example, every 1 standard deviation (SD) servings/day increase in egg intake during pregnancy was associated with 4.4 % (95 % CI: 0.6, 8.4), 3.3 % (0.1, 6.7), and 10.3 % (5.6, 15.2) higher plasma PFOS, PFOA, and PFDA concentrations respectively. Similarly, every 1 SD servings/day increase in white rice intake during pregnancy was associated with 7.5 % (95 % CI: -0.2, 15.8) and 12.4 % (4.8, 20.5) greater milk PFOS and PFOA concentrations, respectively. Our study suggests that certain dietary factors during pregnancy may contribute to higher PFAS concentrations in maternal plasma and human milk, which could inform interventions to reduce PFAS exposure for both birthing people and offspring.

Per- and polyfluoroalkyl substances (PFAS) in senior care facilities and older adult residents.

Per- and polyfluoroalkyl substances (PFAS) are fluorinated organic compounds used in a variety of consumer products and industrial applications that persist in the environment, bioaccumulate in biological tissues, and can have adverse effects on human health, especially in vulnerable populations. In this study, we focused on PFAS exposures in residents of senior care facilities. To investigate relationships between indoor, personal, and internal PFAS exposures, we analyzed 19 PFAS in matched samples of dust collected from the residents' bedrooms, and wristbands and serum collected from the residents. The median ∑PFAS concentrations (the sum of all PFAS detected in the samples) measured in dust, wristbands, and serum were 120 ng/g, 0.05 ng/g, and 4.0 ng/mL, respectively. The most abundant compounds in serum were linear- and branched-perfluorooctane sulfonic acid (L-PFOS and B-PFOS, respectively) at medians of 1.7 ng/mL and 0.83 ng/mL, respectively, followed by the linear perfluorooctanoic acid (L-PFOA) found at a median concentration of 0.59 ng/mL. Overall, these three PFAS comprised 80 % of the serum ∑PFAS concentrations. A similar pattern was observed in dust with L-PFOS and L-PFOA found as the most abundant PFAS (median concentrations of 13 and 7.8 ng/g, respectively), with the overall contribution of 50 % to the ∑PFAS concentration. Only L-PFOA was found in wristbands at a median concentration of 0.02 ng/g. Significant correlations were found between the concentrations of several PFAS in dust and serum, and in dust and wristbands, suggesting that the indoor environment could be a significant contributor to the personal and internal PFAS exposures in seniors. Our findings demonstrate that residents of assisted living facilities are widely exposed to PFAS, with several PFAS found in blood of each study participant and in the assisted living environment.

Lanthanide metal-organic framework-based surface molecularly imprinted polymers ratiometric fluorescence probe for visual detection of perfluorooctanoic acid with a smartphone-assisted portable device.

Perfluorooctanoic acid (PFOA) poses a threat to the environment and human health due to its persistence, bioaccumulation, and reproductive toxicity. Herein, a lanthanide metal-organic framework (Ln-MOF)-based surface molecularly imprinted polymers (SMIPs) ratiometric fluorescence probe (Eu/Tb-MOF@MIPs) and a smartphone-assisted portable device were developed for the detection of PFOA with high selectivity in real water samples. The integration of Eu/Tb MOFs as carriers not only had highly stable multiple emission signals but also prevented deformation of the imprinting cavity of MIPs. Meanwhile, the MIPs layer preserved the fluorescence of Ln-MOF and provided selective cavities for improved specificity. Molecular dynamics (MD) was employed to simulate the polymerization process of MIPs, revealing that the formation of multiple recognition sites was attributed to the establishment of hydrogen bonds between functional monomers and templates. The probe showed a good linear relationship with PFOA concentration in the range of 0.02-2.8 µM, by giving the limit of detection (LOD) of 0.98 nM. Additionally, The red-green-blue (RGB) values analysis based on the smartphone-assisted portable device demonstrated a linear relationship of 0.1-2.8 µM PFOA with the LOD of 3.26 nM. The developed probe and portable device sensing platform exhibit substantial potential for on-site detecting PFOA in practical applications and provide a reliable strategy for the intelligent identification of important targets in water environmental samples.

Nationwide distribution of perfluoroalkyl ether carboxylic acids in Chinese diets: An emerging concern.

With the phase-out of perfluorooctanoic acid (PFOA) and its replacement by perfluoroalkyl ether carboxylic acids (PFECAs), there is a potential for increased exposure to various new PFECAs among the general population in China. While there are existing studies on dietary exposure to legacy perfluoroalkyl and polyfluoroalkyl substances (PFASs), research on dietary exposure to PFECAs, especially among the general Chinese populace, remains scarce. In the present study, we investigated the distribution of PFECAs in dietary sources from 33 cities across five major regions in China, along with the associated dietary intake. Analysis indicated that aquatic animal samples contained higher concentrations of legacy PFASs compared to those from terrestrial animals and plants. In contrast, PFECAs were found in higher concentrations in plant and terrestrial animal samples. Notably, hexafluoropropylene oxide dimer (HFPO-DA) was identified as the dominant compound in vegetables, cereals, pork, and mutton across the five regions, suggesting widespread dietary exposure. PFECAs constituted the majority of PFAS intake (57 %), with the estimated daily intake (EDI) of HFPO-DA ranging from 2.33 to 3.96 ng/kg bw/day, which corresponds to 0.78-1.32 times the reference dose (RfD) (3.0 ng/kg bw/day) set by the United States Environmental Protection Agency. Given the ubiquity of HFPO-DA and many other PFECAs in the nationwide diet of China, there is an urgent need for further research into these chemicals to establish relevant safety benchmarks or consumption advisory values for the diet.

Trend of PFAS concentrations and prediction of potential risks in Taihu Lake of China by AQUATOX.

Per- and polyfluoroalkyl substances (PFAS) are recognized as emerging environmental pollutants due to their high persistence and toxicities to humans and animals. Understanding the temporal trend of PFAS in the environment is important for their pollution control and making appropriate policies. Many studies have reported the PFAS concentrations in Taihu Lake, the third largest lake in China, while their temporal trend during the years was seldom investigated. This study summarizes the PFAS concentrations in the water, sediment and organisms in Taihu Lake from 2009 to 2020 to depict their temporal trends. Meanwhile, the ecological model of AQUATOX was applied to evaluate and predict the potential risks of PFAS from 2012 to 2030. The results showed that the total PFAS concentrations varied but without distinct increase or decrease in both water and sediment during the years, while PFAS concentrations in organisms significantly decreased. The yearly mean concentrations of perfluorooctanoic acid (PFOA) and perfluorooctane sulfonate (PFOS) in the water were 21.7-25.4 ng/L and 9.7-26.5 ng/L respectively, lower than the Standards for Drinking Water Quality of China and the suggested water quality criteria to protect the aquatic organisms. In sediment, PFOA and PFOS concentrations were 0.16-0.69 ng/g and 0.15-0.82 ng/g respectively, much lower than the recommended sediment quality guideline values. Based on the AQUATOX prediction, there will be no major threats caused by PFAS to the growth of biota in Taihu Lake in the near future, while the biomass of some species (e.g. carp) will be affected under the perturbation of PFAS. Both field investigation and AQUATOX simulation showed that PFOS concentrations in invertebrates and fish descend steadily, while no remarkable decrease in PFOA concentrations was expected. This study suggests a decreasing ecological risk of PFAS in Taihu Lake, while highlights the necessity of continuous monitoring of PFAS contamination.

Recovery of perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) from water using foam fractionation with whey soy protein.

Perfluorooctane sulfonate (PFOS) and perfluorooctanoate (PFOA) are persistent anthropogenic chemicals that are widely distributed in the environment and pose significant risks to human health. Foam fractionation has emerged as a promising method to recover PFOS/PFOA from water. However, PFOS/PFOA concentrations in wastewater are often inadequate to generate stable foams due to their high critical micelle concentrations and the addition of a cosurfactant is necessary. In this study, we developed whey soy protein (WSP) as a green frother and collector derived from soybean meal (SBM), which is an abundant and cost-effective agro-industrial residue. WSP exhibited excellent foaming properties across a wide pH range and demonstrated strong collection capabilities that enhanced the recovery of PFOS/PFOA. The mechanism underlying this collection ability was elucidated through various methods, revealing the involvement of electrostatic attraction, hydrophobic interaction, and hydrogen bonding. Furthermore, we designed a double plate internal to improve the enrichment of PFOS/PFOA by approximately 2.3 times while reducing water recovery. Under suitable conditions (WSP concentration: 300 mg/L, pH: 6.0, air flowrate: 300 mL/min), we achieved high recovery percentages of 94-98% and enrichment ratios of 7.5-12.8 for PFOS/PFOA concentrations ranging from 5 to 20 mg/L. This foam fractionation process holds great promise for the treatment of PFOS/PFOA and other per- and polyfluoroalkyl substances.