Advances in perfluoro-alkylated compounds (PFAS) detection in seafood and marine environments: A comprehensive review on analytical techniques and global regulations.

Per- and poly-fluoroalkyl substances (PFAS) are persistent organic pollutants that severely threaten the environment and human health due to their distinct chemical composition, extensive production, widespread distribution, bioaccumulation in nature, and long-term persistence. This review focuses on the occurrence and sources of PFAS in seafood, with a particular emphasis on advanced detection methods viz. nanoparticle-based, biosensor-based, and metal-organic frameworks-based, and mass spectrometric techniques. The challenges associated with these advanced detection technologies are also discussed. Recent research and regulatory updates about PFAS, including hazardous and potential health effects, epidemiological studies, and various risk assessment models, have been reviewed. In addition, the need for global monitoring programs and regulations on PFAS are critically reviewed by underscoring their crucial role in protecting human health and the environment. Further, approaches for reducing PFAS in seafood are highlighted with future innovative remediation directions. Although advanced PFAS analytical methods are available, selectivity, sample preparation, and sensitivity are still significant challenges associated with detection of PFAS in seafood matrices.  Moreover, crucial research gaps and solutions to essential concerns are critically explored in this review.

Per- and polyfluoroalkyl substances (PFAS) in drinking water in Southeast Los Angeles: Industrial legacy and environmental justice.

Per- and polyfluoroalkyl substances (PFAS) are persistent chemicals of increasing concern to human health. PFAS contamination in water systems has been linked to a variety of sources including hydrocarbon fire suppression activities, industrial and military land uses, agricultural applications of biosolids, and consumer products. To assess PFAS in California tap water, we collected 60 water samples from inside homes in four different geographic regions, both urban and rural. We selected mostly small water systems with known history of industrial chemical or pesticide contamination and that served socioeconomically disadvantaged communities. Thirty percent of the tap water samples (18) had a detection of at least one of the 32 targeted PFAS and most detections (89 %) occurred in heavily industrialized Southeast Los Angeles (SELA). The residents of SELA are predominately Latino and low-income. Concentrations of perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) ranged from 6.8 to 13.6 ng/L and 9.4-17.8 ng/L, respectively in SELA and were higher than State (PFOA: 0.007 ng/L; PFOS: 1.0 ng/L) and national health-based goals (zero). To look for geographic patterns, we mapped potential sources of PFAS contamination, such as chrome plating facilities, airports, landfills, and refineries, located near the SELA water systems; consistent with the multiple potential sources in the area, no clear spatial associations were observed. The results indicate the importance of systematic testing of PFAS in tap water, continued development of PFAS regulatory standards and advisories for a greater number of compounds, improved drinking-water treatments to mitigate potential health threats to communities, especially in socioeconomically disadvantaged and industrialized areas.

Infants exposure to chemicals in diapers: A review and perspective.

Diapers are a staple care product for infants, yet concerns persist regarding the potential risks posed by dermal exposure to chemicals through their usage. This review provides a comprehensive summary of reported chemicals, highlighting the frequent detection of polychlorodibenzo-p-dioxins (PCDDs), phthalates (PAEs), volatile organic compounds (VOCs), polycyclic aromatic hydrocarbons (PAHs), bisphenols (BPs), organotins, and heavy metals. Disposable diapers commonly exhibit higher concentrations of VOCs, PAEs, BPs, and heavy metals than other chemicals. Our estimation reveals formaldehyde as posing the highest dermal exposure dose, reaching up to 0.018 mg/kg bw/day. Conversely, perfluorooctanoic acid (PFOA) exhibits lower exposure, but its non-cancer hazard quotient (0.062) is the highest. In most scenarios, the risk of chemical exposure through diapers for infants is deemed acceptable, while the risk is higher under some extreme exposure scenarios. Using the cancer slope factor recently suggested by U.S. EPA, the cancer risk in diapers raised by PFOA is 5.5 × 10-5. It should be noted that our estimation is approximately 1000-10,000 folds lower than some previous estimations. The high uncertainties associated with exposure and risk estimations are primarily raised by unclear parameters related to chemical migration coefficients, absorption factors, concentrations, and toxicity data for skin exposure, which requires research attention in future. Besides that, future research endeavors should prioritize the identification of potential toxic chemicals and the development of hygiene guidelines and standards.

Aggregated health risk assessment of perfluoroalkyl acids migrated from convenience food contact materials.

Ingestion of perfluoroalkyl acids (PFAAs) via contaminated food contact materials (FCMs) is an important human exposure source. This study adopts a toxicity equivalent approach to evaluate the collective health risk of multiple PFAAs in FCMs. A comprehensive extraction and analysis of 21 PFAAs in FCMs was performed. Among the analyzed substances, 15 PFAAs were detected. Migration experiment using three food simulants revealed the migration range of seven PFAAs from FCMs into the simulant to be 0.47-46.7 ng/cm2. The hazard quotient results suggest minimal health risk, except for 9% of packaged samples where perfluorooctanoic acid (PFOA) poses a higher risk. Utilizing PFOA toxic equivalent concentrations, comprehensive risk calculations showed ∼77% of samples potentially posing elevated health risks due to PFAA exposure. This emphasizes the substantial contribution of PFAAs beyond PFOA and underscores the importance of considering them in related assessments. The aggregated risk assessment reflects actual exposure circumstances more accurately.

Occurrence and health risk assessment of PFAS and possible precursors: a case study in a drinking water treatment plant and bottled water (south Catalonia, Spain).

The presence of PFAS in drinking water may pose a serious threat to human health. This study aims to determine the levels of these compounds and their precursors in water samples from a drinking water treatment plant (DWTP) located in l'Ampolla (Spain) and to assess their fate. Additionally, ten Spanish bottled waters were analyzed to compare the occurrence of PFAS in the mentioned matrices and in drinking water. Off-line solid phase extraction (SPE) followed by liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) was applied to determine 26 PFAS and PFAS precursors after a total oxidizable precursor assay. The analytical method presents low quantification limits (0.25-5 ng/L). A total PFAS concentration of up to 16 ng/L in all the DWTP samples was obtained, and 6:2 FTS was the only precursor detected. Results are close to the quantification limits, resulting in a high degree of uncertainty, and for this, it is difficult to evaluate the DWTP PFAS removal efficiency. Regarding bottled water, total PFAS concentration found was up to 12 ng/L in one of ten samples, with no precursors detected. Exposure assessment revealed that there is no risk associated with the ingestion of the samples analyzed. Moreover, there were no differences in terms of risk between drinking water from l'Ampolla DWTP and bottled water.

Rapid and simultaneous determination of ultrashort-, short- and long- chain perfluoroalkyl substances by a novel liquid chromatography mass spectrometry method.

Per- and Polyfluoroalkyl Substances (PFAS) are a group of persistent organic pollutants that have received considerable attention from public and regulatory groups. Due to regulations of long-chain PFAS, the use of short-chain and ultrashort-chain PFAS is rapidly growing. Thus, there is an urgent need to develop quantitative methods for determining PFAS with different chain lengths in various environmental matrices. This study introduces an innovative liquid chromatography-mass spectrometry (LC-MS) system combining large volume injection (LVI) and online solid phase extraction (SPE). This system incorporates three columns: a reverse-phase (RP) column, a weak anion exchange (WAX) trap column, and a hybrid HILIC/ion-exchange (HILIC/IE) column, controlled by two valves. With valve switching, ultrashort-chain PFAS that are not retained by the RP column are enriched by the trap column, while other PFAS are separated by the RP column. The trapped ultrashort PFAS are then transferred to the HILIC/IE column for further separation. The LVI significantly enhances the method's sensitivity, allowing for rapid and simultaneous determination of ultrashort-, short- and long- chain PFAS in aqueous samples. The matrix effects from various environmental samples were evaluated, and the results indicate that this unique LC-MS method is suitable for analyzing all chain-length PFAS in various matrices, including surface water, sewage effluent, and seawater. Finally, this novel LC-MS method was applied to quantify PFAS in various water samples.

Fugacity model covering abiotic and biotic matrices to investigate the transfer and fate of perfluoroalkyl acids in a large shallow lake of eastern China.

Solving the challenges faced during the measurement of the cross-interface transfer of perfluoroalkyl acids (PFAAs) in lakes is crucial for clarifying environmental behaviours of these chemicals and their efficient governance. This study developed a multimedia fugacity model based on the quantitative water-air-sediment interaction (QWASI) covering abiotic/biotic matrices to investigate the cross-interface transfer and fate of PFAAs in Luoma Lake, a typical PFAA-contaminated shallow lake in eastern China. The accuracy and reliability of the established model were confirmed using Percent bias and Monte Carlo simulation, respectively. Using the QWASI model, the multimedia transfer of the PFAAs and their accumulation and persistence in different sub-compartments were described and measured, and the differences among individual PFAAs were explored. The simulation results showed that the sedimentation and resuspension of PFAAs were the most intense cross-interfacial transfers, and the sediments served as a chemical sink in the long term. A significant negative correlation of NC-F (the number of CF bonds) with the relative outflow flux (TW·out-ct) but a positive correlation with the relative net transfer across the interface between water and aquatic plants (Tp-ct) was detected, indicating that the PFAA migration capacity decreased but the bioaccumulation potential increased with the CF bond number. The persistence in water (Pw) of individual PFAAs ranged from 19.65d (PFOA) to 32.22d (PFOS), with an average of 26.15d; their persistence in sediment (Ps) ranged from 432d (PFBA) to 3216d (PFOS), with an average of 1524d, increasing linearly with an increase in NC-F. The water advection flows into and out of the lake (QW·in and QW·out), the PFAA concentration of water inflow (CW·in), and bioconcentration factor of aquatic plants (BCFp) were the primary parameters sensitive to PFAAs in all sub-compartments, which are essential indexes for exploring promising remediation pathways for lacustrine PFAA contamination based on the fugacity model simulation.

Leaching of per- and polyfluoroalkyl substances (PFAS) from food contact materials with implications for waste disposal.

Leaching of per- and polyfluoroalkyl substances (PFAS) during the post-consumer disposal of food contact materials (FCMs) poses a potential environmental threat but has seldom been evaluated. This study characterized the leaching behavior of PFAS and unidentified precursors from six common FCMs and assessed the impact of environmental conditions on PFAS release during disposal. The total concentration of 21 PFAS ranged from 3.2 to 377 ng/g in FCMs, with PFAS leachability into water varying between 1.1-42.8 %. Increasing temperature promoted PFAS leaching, with leached nine primary PFAS (∑9PFAS) reaching 46.3, 70.4, and 102 ng/L at 35, 45, and 55 â„ƒ, respectively. Thermodynamic analysis (∆G>0, ∆H>0, and ∆S<0) indicated hydrophobic interactions control PFAS leaching. The presence of dissolved organic matter in synthetic leachate increased the leached ∑9PFAS from 47.1 to 103 ng/L but decreased PFBS, PFOS, and 6:2 FTS leaching. The total release of seven perfluorocarboxylic acids (∑7PFCAs) from takeaway food packaging waste was estimated to be 0.3-8.2 kg/y to landfill leachate and 0.6-15.4 kg/y to incineration plant leachate, contributing 0.2-4.8 % and 0.1-3.2 % of total ∑7PFCAs in each leachate type. While the study presents a refined methodology for estimating PFAS release during disposal, future research is needed on the indirect contribution from precursors.

Sampling of per- and polyfluoroalkyl substances in drainage water from a waste management facility.

Per- and polyfluoroalkyl substances (PFAS) have been used for decades in a broad range of consumer products and industrial applications. A variety of waste and products containing PFAS inevitably end up at waste management facilities when they are no longer considered useful. Drainage water samples (n = 157) were collected from eight subsections at a waste management facility in Sweden and analyzed for 23 PFAS and extractable organofluorine (EOF). Two different sampling methods were used, grab sampling (n = 32, without filtration) and composite sampling (n = 8, produced by pooling 16 filtered samples taken at the same subsection). Although PFAS have been studied at waste sites, the information is scarce regarding how the concentrations and homologue profiles could differ within the sites. In this study, we investigated if composite sampling could be an alternative to grab sampling for PFAS monitoring purposes. Herein, the PFAS concentrations ranged from <1 to 22 µg/L; the grab samples showed systematic higher concentrations than their corresponding composite sample. Short-chain perfluoroalkyl sulfonic acids (C4 and C5) were the largest contributing sub-class, followed by short-chain perfluoroalkyl carboxylic acids (C4 to C6). EOF was measured up to approximately 140 µg/L F with 99% being unexplained by the fluorine mass balance analysis. The results from this study showed that both sampling methods were comparable for target analysis and that 11 compounds represented most of the PFAS concentrations. However, the discrepancy between the sampling methods was greater for EOF analysis and may be due to the preparation of composite samples and/or due to fluctuating discharges during the sampling period. Composite sampling was observed to be comparable to grab sampling for target analysis.

Examining a decade-long trend in exposure to per- and polyfluoroalkyl substances and their correlation with lipid profiles: Insights from a prospective cohort study on the young Taiwanese population.

Per- and polyfluoroalkyl substances (PFAS) are artificial chemicals extensively utilized in everyday products, and numerous cross-sectional epidemiological studies consistently link PFAS exposure with lipid profiles across diverse populations and age groups. In longitudinal studies, the findings also indicate a positive correlation between PFAS and lipid profiles; however, this association remains unexplored in adolescents and young adults. Notably, previous research has predominantly focused on conventional lipid biomarkers, with limited exploration of the relationship between PFAS and diverse lipoprotein subfractions. Furthermore, there is a lack of comprehensive investigation into the temporal trends in PFAS concentrations in Taiwan. To address this research gap, we conducted a prospective study following 592 adolescents and young adults (12-30 years old at enrollment) from the YOung TAiwanese Cohort (YOTA) over a duration of 10 years. During the follow-up period, we measured 11 types of PFAS and various lipid profile biomarkers (low-density lipoprotein cholesterol (LDL-C), small dense LDL-C (sdLDL-C), low-density lipoprotein triglyceride (LDL-TG), high-density lipoprotein cholesterol (HDL-C), HDL3-C, lipoprotein(a), triglyceride). Our results revealed a general decline in PFAS concentrations in the study population. Regarding the correlation between the average levels (averaged across the initial and second tracking periods) of PFAS and lipid profiles (during the second tracking period), we observed positive correlations with total cholesterol and LDL-C for perfluorononanoic acid (PFNA), perfluoroundecanoic acid (PFUdA), perfluorododecanoic acid (PFDoA), N-methylperfluorooctane sulfonamide acetic acid (N-MeFOSAA), and the sum of PFAS (sum of the 11 kinds of PFAS). Additionally, average levels of PFUdA, N-MeFOSAA, and the sum of PFAS exhibited positive associations with sdLDL-C. This study unveiled an overall decrease in PFAS concentrations and underscores a potential link between PFAS exposure and adverse changes in lipid profiles among young populations, emphasizing the need for further exploration into the mechanisms of PFAS on lipid metabolism and atherosclerosis.

Concentration and health risk assessment of per- and polyfluoroalkyl substances in cosmetic and personal care products.

Per and polyfluoroalkyl substances (PFAS) are toxicologically concerning because of their potential to bioaccumulate and their persistence in the environment and the human body. We determined PFAS levels in cosmetic and personal care products and assessed their health risks. We investigated the trends in concentrations and types of PFAS contaminants in cosmetic and personal care products before and after perfluorooctane sulfonate (PFOS) and perfluorooctanoic acid (PFOA) were added to the list of persistent organic pollutants. The total PFAS concentration ranged from 1.98 to 706.75 ng g-1. The hazard quotients (HQs) for PFOA, PFOS and perfluorobutanesulfonic acid (PFBS) were lower than 1, indicating no appreciable risk to consumers. Assuming the simultaneous use of all product types and the worst-case scenario for calculations, perfluoroalkyl carboxylic acids and perfluoroalkane sulfonic acids (PFSAs) also had hazard indices lower than 1. We found that adverse effects are unlikely to occur when each type of cosmetic is used separately, or even when all product types are used together. Nevertheless, the persistence and bioaccumulation characteristics of additional PFAS present in cosmetics continue to be a cause for concern. Further research is necessary to investigate the long-term impacts of using such cosmetics and the associated risks to human health.

Biochar from paddy field - A solution to reduce PFAS pollution in the environment.

Generally, activated carbons demonstrated a notable ability to capture long-chain PFAS, but exhibited relatively lower effectiveness for short-chain PFAS. Thirteen commercially available activated carbons in Japan underwent testing for their adsorption capacity of PFAS in water. The activated carbon derived from rice husk, Triporous™-PFAS, exhibited the highest adsorption capacity (over 95%) for PFAS from ultrashort-chain (perfluorocarbon chain: C1 for perfluorocarboxylic acid (PFCA) and C2 for perfluoroalkane sulfonic acid (PFSA)) to long-chain PFAS (C13 for PFCA and C10 for PFSA). An earlier lysimeter study highlighted Andosol, representative soil in Japan, as a potential medium for removing PFAS from irrigation water. Considering cultivating rice on Andosol fields and producing biochar from rice husks and rice straw, a new rice cultivation system is proposed. This system aims to facilitate continuous removal of PFAS from the environment in Asia. Japanese rice cultivation system produces not only rice but also biochar to remove PFAS from water circulation system. The total fluorine content in the tested activated carbon materials ranged from 0.18 to 38 µg g-1 F. Based on the results from background F blank and adsorption capacity, TriporousTM-PFAS-F was shown to be an option to lower the method detection limit for a proposed international standard method for measuring total PFAS.

Occurrence of perfluoroalkyl compounds in commercially available baby food produced in different European countries - levels, dietary intake, and exposure assessment.

The presence of per- and polyfluoroalkyl substances (PFASs) in commercial baby food products from various European countries was investigated in this study. A total of 96 samples were collected and analyzed to assess PFASs levels, composition profiles, and potential dietary intake among infants. The results indicated detectable levels of PFASs in the sampled baby food products, with carboxylic acid prevalence over sulfonic acids. Among the various baby food groups studied, dry cereals exhibited the highest PFASs concentrations. This finding emphasizes the need for further monitoring and investigation of PFASs contamination in this specific food category. While the concentrations detected were generally low, they indicated the widespread presence of PFASs in various types of baby food. Furthermore, a preliminary exposure assessment was conducted on the basis of the measured PFASs concentrations, providing an initial insight into the potential exposure levels among infants from three months to three years old. Calculations based on two scenario types revealed the best-case scenario likely underestimating actual exposure, while the worst-case scenario occasionally exceeded the limits set by the governmental institutions. Further research is needed to understand the sources, pathways, and potential health effects of PFASs exposure in this vulnerable population.

Dual-mode electrochemical and SERS detection of PFAS using functional porous substrate.

Human activity is the cause of the continuous and gradual grooving of environmental contaminants, where some released toxic and dangerous compounds cannot be degraded under natural conditions, resulting in a serious safety issue. Among them are the widely occurring water-soluble perfluoroalkyl and polyfluoroalkyl substances (PFAS), sometimes called "forever chemicals" because of the impossibility of their natural degradation. Hence, a reliable, expressive, and simple method should be developed to monitor and eliminate the risks associated with these compounds. In this study, we propose a simple, express, and portable detection method for water-soluble fluoro-alkyl compounds (PFOA and GenX) using mutually complementary methods: electrochemical impedance spectroscopy (EIS) and surface-enhanced Raman spectroscopy (SERS). To implement our method, we developed special substrates based on porous silicon with a top-deposited plasmon-active Au layer by subsequently grafting -C6H4-NH2 chemical moieties to provide surface affinity toward negatively charged water-soluble PFAS. Subsequent EIS utilization allows us to perform semiquantitative detection of PFOA and GenX up to 10-10 M concentration because surface entrapping of PFAS leads to a significant increase in the electrode-electrolyte charge-transfer resistance. However, distinguishing by EIS whether even PFAS were entrapped was impossible, and thus the substrates were subsequently subjected to SERS measurements (allowed by surface plasmon activity due to the presence of a porous Au layer), clearly indicating the appearance of characteristic C-F vibration bands.

Per- and polyfluoroalkyl substances (PFAS) in homegrown crops: Accumulation and human risk assessment.

Homegrown crops can present a significant exposure source of per- and polyfluoroalkyl substances (PFAS) to humans. Field studies studying PFAS accumulation in multiple vegetable food categories and examining the potential influence of soil characteristics on vegetable bioavailability under realistic exposure conditions are very scarce. Crop PFAS accumulation depends on a complex combination of factors. The physicochemical differences among the numerous PFAS makes risk assessment very challenging. Thus, simplification of this complexity into key factors that govern crop PFAS accumulation is critical. This study analyzed 29 targeted legacy, precursor and emerging PFAS in the vertical soil profile (0-45 cm depth), rainwater and edible crop parts of 88 private gardens, at different distances from a major fluorochemical plant. Gardens closer to the plant site showed higher soil concentrations which could be linked with historical and recent industrial emissions. Most compounds showed little variation along the soil depth profile, regardless of the distance from the plant site, which could be due to gardening practices. Annual crops consistently accumulated higher sum PFAS concentrations than perennials. Highest concentrations were observed in vegetables, followed by fruits and walnuts. Single soil-crop relationships were weak, which indicated that other factors (e.g., porewater) may be better measures of bioavailability in homegrown crop accumulation. Regression models, which additionally considered soil characteristics showed limited predictive power (all R2 ≤ 35%), possibly due to low variability in crop concentrations. Human intake estimations revealed that the PFAS exposure risk via crop consumption was similar nearby and remotely from the plant site, although the contribution to the overall dietary exposure can be relatively large. The tolerable weekly intake was frequently exceeded with respect to fruit and vegetable consumption, thus potential health risks cannot be ruled out.

Clinical Implications of New Drinking Water Regulation for "Forever Chemicals".

This Viewpoint describes new maximum contaminant levels set by the Environmental Protection Agency for specific perfluoroalkyl and polyfluoroalkyl substances (PFASs) and discusses the role clinicians can play in addressing their patients' PFAS health concerns.

Programming of a Portable Digital Monitoring System-Integrated DNA Aptamer Reversely Regulated Oxidase-Like Nanozyme for Real-Time Dynamic Analysis of Atmospheric Perfluorooctanoic Acid.

Timely and efficient analysis of the fluorinated per- and polyfluoroalkyl substances (PFAS) in an atmospheric environment is critical to environmental pollution traceability, early warnings, and governance. Here, a portable, reliable, and intelligent digital monitoring device for onsite real-time dynamic analysis of atmospheric perfluorooctanoic acid (PFOA) is proposed. The sensing mechanism is attributed to the oxidase-like activity of PtCoNPs@g-C3N4 that is reversely regulated by the surface modification of a PFOA-recognizable DNA aptamer, engineering a PFOA-activated oxidase-like activity of nanozyme (Apt-PtCoNPs@g-C3N4) to combine the nonfluorescence o-phenylenediamine (OPD) as the dual-modality response system. The present PFOA interacts with its DNA aptamer and dissociates from the surface of Apt-PtCoNPs@g-C3N4, restoring the oxidase-like activity of PtCoNPs@g-C3N4 to oxidize OPD into yellow fluorescence 2,3-diphenylaniline (DAP), thereby observing a PFOA-triggered colorimetric as well as fluorescence dual-modality change. Then, a hydrogel kit-programmed Apt-PtCoNPs@g-C3N4 + OPD system is used as the sensitive element to incorporate into this homemade portable device, automatically gathering and processing the PFOA-triggered hydrogel colorimetric and fluorescence image gray values by our self-weaving software, ultimately realizing the onsite real-time dynamic analysis of atmospheric PFOA surrounding a fluorochemical production plant. This work provides a direction and theoretical foundation for designing portable onsite screening devices that cater to other atmospheric contaminants detection requirements.

Development and Application of a Liquid Chromatography-Tandem Mass Spectrometry Method for the Analysis of 20 Perfluoroalkyl Substances in Fruit and Vegetables at Sub-Parts-per-Trillion Levels.

In response to the European Food Safety Authority's establishment of a tolerable weekly intake (TWI) for the sum of PFOA, PFNA, PFHxS, and PFOS, a method was developed to quantify and confirm 20 PFASs at the sub-parts-per-trillion level in fruit and vegetables. Improved sensitivity was achieved by (i) increasing the sample intake, (ii) decreasing the solvent volume in the final extract, and (iii) using a highly sensitive mass spectrometer. Except for PFTrDA, target PFASs could be quantitatively determined with an apparent recovery of 90-119%, limits of quantitation down to 0.5 ng/kg, and a relative standard deviation under within-laboratory reproducibility conditions of <28%. The method was successfully applied to 215 fruit and vegetable samples obtained from local grocery stores and markets. Leafy vegetables prove to be the main vegetable category responsible to PFAS exposure, mainly of PFOA, followed by PFHpA and PFHxA.

Rapid Determination of 12 Classes of Per- and Polyfluoroalkyl Substances in Water Samples from Environmental Forensic Cases.

The widespread use of per- and polyfluoroalkyl substances (PFASs) with different physico-chemical properties poses a great threat to the environment and human health. Simultaneous detection of different classes of PFASs is a difficult task, especially for rapid analysis of polluted water samples in environmental forensic cases. In this study, a simple sample preparation ultrahigh-performance liquid chromatography coupled with quadrupole Orbitrap high-resolution mass spectrometry was established for the detection of PFASs in a wide range of water matrices. By optimizing the conditions of pretreatment and the parameters of the instrument, the developed method provided good linearity of calibration standards (R2 > 0.99), and demonstrated excellent MLOQ (0.008-1.2 µg/L), with spiked recoveries ranging from 57.7% to 151% for 47 targets in surface water samples, and from 45.7 to 165% for 46 targets in ground and waste water samples, respectively. This method required an injection volume of 3 µL and an analysis time of only 18 min per sample. The validation method was successfully applied to the analysis of 20 environmental water samples, in which 15 target substances with different concentrations were detected, with total concentrations of 0.082 to 262.455 µg/L. The method is simple and exclusive, and can rapidly confirm the occurrence of PFASs in different water samples, providing a convenient and fast high-throughput analysis, which is especially suitable for the application in the environmental forensic investigation of PFASs pollution.

Decontamination promotes the release of incorporated organic contaminants in hair: Novel insights into non-invasive biomonitoring.

Human hair is increasingly employed as a non-invasive biomonitoring matrix for exposure to organic contaminants (OCs). Decontamination procedures are generally needed to remove external contamination from hair prior to analysis of OCs. Despite various existing decontamination protocols, their impacts on internally incorporated (endogenous) OCs in hair remain poorly understood. This study aims to quantitatively assess the impact of decontamination procedures on endogenous OCs in hair, and investigate optimal decontamination processes and factors influencing the removal of endogenous OCs. In this study, guinea pig was exposed to 6 OCs (triphenyl phosphate (TPHP), tris(1,3-dichloro-2-propyl) phosphate (TDCPP), and tri-n-butyl phosphate (TNBP), bisphenol A (BPA), perfluorooctanoic acid (PFOA), and phenanthrene (PHE)), and 6 decontamination procedures with different solvents (methanol, n-hexane, acetone, ultrapure water, Triton X-100, and sodium dodecyl sulfate) were used to rinse exposed guinea pig hair. All OCs and three metabolites (diphenyl phosphate (DPHP), dibutyl phosphate (DBP), and bis(1,3-dichloro-2-propyl) phosphate (BDCPP)) were detected in the majority of washing solutions. The decontamination procedures apparently resulted in the release of endogenous OCs from hair. The percentages of residual OCs in hair exhibited a linear or exponential decrease with more washing cycles. Furthermore, the residuals of OCs in hair washed with organic and aqueous solvents showed negative correlations with molecular weight, polarizability, and their initial concentrations. Although these findings need to be validated with a broader range of OCs, the results obtained in this study provide compelling evidence that current hair decontamination procedures have significant impacts on the analysis of endogenous OCs in hair. Therefore, it is important to interpret quantitative data on hair OC concentrations with caution and to thoroughly consider each decontamination procedure during analysis.