The 6:2 chlorinated polyfluoroalkyl ether sulfonic acids (6:2 Cl-PFAES), 2,3,3,3-tetrafluoro-2-(1,1,2,2,3,3,3-heptafluoropropoxy)-propanoic acid (HFPO-DA) and perfluoroethylcyclohexane sulfonate (PFECHS) are emerging per- and polyfluoroalkyl substances (PFASs) that are being applied to replace phased-out PFASs, which have high persistency, high bioaccumulation potential and high toxicity. Recently, these emerging PFASs were observed in estuary and marine areas with a pollution level of ng/L. In this study, three levels (10 ng L⁻¹, 100 ng L⁻¹ and 1000 ng L⁻¹) for these PFASs were selected to investigate the response of marine Chlorella sp. to 14 days of exposure. The growth of Chlorella sp. was significantly inhibited by each PFAS over time. Treatments with 1000 ng/L exposure caused the most severe reduction in growth for each PFAS treatment. For the first half of the experimental period (from Day 0 to Day 6), the influence of each PFAS was not significant (p > 0.05). However, treatments with all concentrations of 6:2 Cl-PFAES, HFPO-DA and 1000 ng L⁻¹ PFECHS significantly reduced the growth of Chlorella sp. from Day 8. The superoxide dismutase (SOD) activities in Chlorella sp. were significantly increased (p < 0.05) when exposed to 6:2 Cl-PFAES, HFPO-DA and PFECHS. The catalase (CAT) and peroxidase (POD) activities in Chlorella sp. were significantly inhibited (p < 0.05) by each PFAS. The glutathione (GSH) contents in Chlorella sp. were significantly increased by each PFAS. However, the increases in GSH concentration in Chlorella sp. were low. The inhibition of algal growth was primarily due to the reduction of the activities of CAT and POD. PFECHS had the lowest toxicity among the three PFASs, and it induced less oxidized damage to Chlorella sp. In conclusion, as alternatives to phased-out PFASs, the emerging PFASs are not safe in aquatic environment, and attention should be paid to the management and restriction of these emerging PFASs.

Perfluoroalkyl acids (PFAAs) were measured in aqueous and suspended particulate matter (SPM) fractions in the final effluents from 12 wastewater treatment facilities located around the Connecticut shoreline. Aqueous phase concentrations ranged from 53 to 198 ng/L for ∑PFAAs with ≤7 perfluorinated carbons (CF₂) and 2–73 ng/L for >7 CF₂ PFAAs. Predominant PFAAs associated with effluent derived SPM were perfluorodecanoic acid and perflurorooctane sulfonic acid, detected in 48% and 52% of samples in concentrations ranging from <LOQ–1770 ng/g and <LOQ–2750 ng/g respectively. Based on the range of concentrations detected and the average flow of final effluent to the Long Island Sound (LIS), average total annual PFAA mass loads from wastewater treatment facilities to the LIS is estimated in the range of 70–315 kg/year, with 4–100 kg/year consisting of >7 CF₂ PFAAs. Partitioning coefficients (log KOC) derived for effluent water and SPM phases (4.2 ± 0.3, 4.4 ± 0.4, 5.1 ± 0.2 and 5.3 ± 0.2 for PFOA, PFNA PFDA and PFUnA; 4.5 ± 0.2 and 5.2 ± 0.2 for PFOS and PFHsX respectively) were found to be of similar magnitude to aeration tank particles, though 0.5 to 2 log units greater than sludge solids and to natural system particulates including riverine SPM, estuarine SPM and sediments. Results from this study suggest that effluent derived suspended particulate matter could be an effective vector in the transport of long-chained PFAAs through wastewater treatment into receiving waters, and a potential vector to the local food chain.

Chlorinated polyfluoroalkyl ether sulfonic acids (Cl-PFESAs) caused great concerns recently as novel fluorinated alternatives. However, information on their bioconcentration, bioaccumulation and biomagnification in marine ecosystems is limited. In this study, 152 biological samples including invertebrates, fishes, seabirds and mammals collected from Bohai Sea of China were analyzed to investigate the residual level, spatial distribution, bioaccumulation and biomagnification of Cl-PFESAs. 6:2 Cl-PFESA was found in concentrations ranging from <MDL (method detection limit) to 3.84 ng/g ww and it is the dominant congener when compared with concentrations of 8:2 Cl-PFESA. Compared with other bays and regions, levels of 6:2 Cl-PFESA are relatively high in bivalves and fishes from Liaodong Bay. These levels were also found to tend to increase as compared with those in 2010–2014. Logarithm bioaccumulation factors (BAFs) for 6:2 Cl-PFESA ranged from 2.23 to 4.21, implying the bioaccumulation of this compound. The trophic magnification factor (BMF) for 6:2 Cl-PFESA was determined to be 3.37 in the marine food web, indicating biomagnification potential along the marine food chain.

The concentration distributions, compositional profiles and seasonal variations of 17 perfluoroalkyl acids (PFAAs) in PM₁₀ (particles with aerodynamic diameters < 10 μm) were determined in seven coastal cities of the Bohai and Yellow Seas. The detection rates of perfluorooctanoic acid (PFOA) and short-chain components (perfluoroalkyl carboxylic acids (PFCAs) with ≤7 carbon atoms and perfluoroalkane sulfonic acids (PFSAs) with ≤5 carbon atoms) were much higher than those of other long-chain PFAA species. The annual average concentration of total PFAAs in PM₁₀ ranged from 23.6 pg/m³ to 94.5 pg/m³ for the sampling cities. The monthly mean concentrations of PFAAs in PM₁₀ in some sampling cities reached a peak value in winter, while no significant seasonal differences presented in other cities. High concentrations of PFAAs in the northern cities generally occurred during the local heating period (from November to March). Generally, the dominant components of PFAAs were PFOA and perfluorobutyric acid (PFBA). Some significantly positive correlations (p < 0.01) between the 10 dominant components were revealed in the sampling cities, which implied similar sources and fate behaviors. Based on the simulated 72-hr backward trajectory tracking of air masses, the clustering results demonstrated the sampling cities were affected mainly by the atmospheric transport in sequence from the northwest, the southwest and the open seas, and many transport trajectories of air masses passed by the local fluorine chemical manufacturers in Liaoning, Shandong, Jiangsu, and Hubei Provinces. The estimated average daily intake (ADI) corresponding to the residents in different age groups indicated insignificant contributions to PFOA and perfluorooctane sulfonate (PFOS) exposures by inhalation of PM₁₀ compared to ingestion by daily diet, while the higher ADI of PFOA than the reported levels for adults should be a concern. The calculated hazard ratios (HR) exhibited low noncancer risks by inhalation exposure to PFOA and PFOS in PM₁₀.

This study focused on the occurrence of long-chain perfluorinated chemicals (PFCs) in anaerobically stabilized sewage sludges from 20 municipal WWTPs using current and historic samples to evaluate the levels of PFCs and to identify the relative importance of commercial and industrial sources. A quantitative analytical method was developed based on solvent extraction of the analytes and a LC-MS/MS system. For total perfluoralkyl carboxylates (PFCAs), the concentrations ranged from 14 to 50μg/kg dry matter. Concentrations of perfluorooctane sulfonic acid (PFOS) ranged from 15 to 600μg/kg dry matter. In three WWTPs, the PFOS levels were six to nine times higher than the average values measured in the other plants. These elevated PFOS concentrations did not correlate with higher levels of PFCAs, indicating specific additional local sources for PFOS at these WWTPs. Average concentrations in selected samples from the years 1993, 2002, and 2008 did not change significantly.

The entirety of the sediment bed in lake Tyrifjorden, Norway, is contaminated by per- and polyfluoroalkyl substances (PFAS). A factory producing paper products and a fire station were investigated as possible sources. Fire station emissions were dominated by the eight carbon perfluoroalkyl sulfonic acid (PFSA), perfluorooctanesulfonic acid (PFOS), from aqueous film forming foams. Factory emissions contained PFOS, PFOS precursors (preFOS and SAmPAP), long chained fluorotelomer sulfonates (FTS), and perfluoroalkyl carboxylic acids (PFCA). Concentrations and profiles in sediments and biota indicated that emissions originating from the factory were the main source of pollution in the lake, while no clear indication of fire station emissions was found. Ratios of linear-to branched-PFOS increased with distance from the factory, indicating that isomer profiles can be used to trace a point source. A dated sediment core contained higher concentrations in older sediments and indicated that two different PFAS products have been used at the factory, referred to here as Scotchban and FTS mixture. Modelling, based on the sediment concentrations, indicated that 42–189 tons Scotchban, and 2.4–15.6 tons FTS mixture, were emitted. Production of paper products may be a major PFAS point source, that has generally been overlooked. It is hypothesized that paper fibres released from such facilities are important vectors for PFAS transport in the aquatic environment.

The co-contamination by perfluoroalkyl acids (PFAAs) and heavy metals (HMs) is ubiquitous in the surface environment subjected to sewage irrigation and land application of sludge. However, the joint effects of HMs and PFAAs on plant roots are not well clarified. This study explored the root uptake and acropetal translocation behaviors of C2–C8 PFAAs by wheat (Triticum acstivnm L.) under the co-exposure of copper (Cu). The underlying uptake mechanisms of PFAAs were verified in a defective root system. The results showed that excessive Cu (100–400 μmol/L) damaged the cell membrane of wheat root to increase electrolytic leakage. In the defective root system, the root concentrations of PFAAs decreased by 6%–73% and the decrease rates were negatively associated with the carbon chain length of PFAAs. Along with the decrease in root concentrations of PFAAs, the amount of ultrashort-chain (C2–C3) and short-chain (C4–C6) PFAAs translocated to the shoot also decreased by 45%–84%. In contrast, the acropetal translocation of long-chain (C8) PFAAs, perfluorooctanoic acid (PFOA) and perfluorooctane sulfonic acid (PFOS), was enhanced under Cu exposure due to the increase in root permeability as observed by increased electrolytic leakage. The shoot concentrations of PFOA and PFOS under Cu exposure were up to 5.5 and 11 times higher than those in the control, respectively. These results suggested that PFOA and PFOS could enter wheat root more easily through the breaks caused by Cu exposure and thereby their acropetal transportation to shoot was enhanced. Therefore, the risk of plant accumulation of long-chain PFAAs can be potentially underestimated if without considering the co-contamination with HMs in the environment.

Ny-Ålesund, one of four permanent settlements on Spitsbergen in Svalbard, is a research town that includes scientific institutes from many countries. Because of daily-used chemicals (e.g., pharmaceutical and personal care products (PPCPs)) used by residents in the area, generated sewage is considered as a point source in the Kongsfjorden. The aim of the present study was to identify and quantify organic pollutants in the effluent and along the shoreline and offshore via target, suspect, and non-target screening using liquid chromatography–high-resolution mass spectrometry. We tentatively identified 30 compounds using the suspect and non-target screening methods in effluent samples from our first visit to the settlement in 2016. Among these, 3 were false positive, 24 were confirmed, and the 3 remaining compounds were not confirmed because of a lack of reference standards. Of the confirmed, 21 were quantifiable and considered target compounds for the 2nd year study. The quantified compounds in the effluent samples in 2017 totaled 17, including PPCPs, pesticides, perfluorinated compounds, and their metabolites. Some of the compounds, such as caffeine, paraxanthine/theophylline, acetaminophen, cetirizine, diethyl toluamide (DEET), and icaridin, were also detected in the receiving seawater. The concentration range was from 4 to 280,000 ng/L in the effluent and 2–98 ng/L in the seawater. Other 24 compounds were tentatively identified in the second-year effluent samples. Five were further confirmed using reference standards. Prioritization was performed on the 47 substances screened in Ny-Ålesund using the exposure and toxicity index. As the result, the top seven substances of concern present were perfluorooctanesulfonic acid (PFOS), triphenyl phosphate (TPHP), irbesartan, DEET, acetaminophen, caffeine, and paraxanthine/theophylline. As the effluent was identified as a source of the concerned organic pollutants, an emission reduction strategy should take place for protection of Arctic Fjorden environment.

Bed sediments and a dated sediment core were collected upstream and downstream from the city of Lyon (France) to assess the spatial and temporal trends of contamination by per- and polyfluoroalkyl substances (PFASs) in this section of the Rhône River. Upstream from Lyon, concentrations of total PFASs (ΣPFASs) in sediments are low (between 0.19 and 2.6 ng g⁻¹ dry weight - dw), being characterized by a high proportion of perfluorooctane sulfonate (PFOS). Downstream from Lyon, and also from a fluoropolymer manufacturing plant, ΣPFASs concentrations reach 48.7 ng g⁻¹ dw. A gradual decrease of concentrations is reported at the coring site further downstream (38 km). Based on a dated sediment core, the temporal evolution of PFASs is reconstructed from 1984 to 2013. Prior to 1987, ΣPFASs concentrations were low (≤2 ng g⁻¹ dw), increasing to a maximum of 51 ng g⁻¹ dw in the 1990s and then decreasing from 2002 to the present day (∼10 ng g⁻¹ dw). In terms of the PFAS pattern, the proportion of perfluoroalkyl sulfonic acids (PFSAs) has remained stable since the 1980s (∼10%), whereas large variations are reported for carboxylic acids (PFCAs). Long chain- (C > 8) PFCAs characterized by an even number of perfluorinated carbons represent about 74% of the total PFAS load until 2005. However, from 2005 to 2013, the relative contribution of long chain- (C > 8) PFCAs with an odd number of perfluorinated carbons reaches 80%. Such changes in the PFAS pattern likely highlight a major shift in the industrial production process. This spatial and retrospective study provides valuable insights into the long-term contamination patterns of PFAS chemicals in river basins impacted by both urban and industrial activities.

The extent of per- and polyfluoroalkyl substances (PFAS) in groundwater surrounding legacy landfills is currently poorly constrained. Seventeen PFAS were analysed in groundwater surrounding legacy landfills in a major Australian urban re-development precinct. Sampling locations (n = 13) included sites installed directly in waste material and down-gradient from landfills, some of which exhibited evidence of leachate contamination including elevated concentrations of ammonia-N (≤106 mg/L), bicarbonate (≤1,740 mg/L) and dissolved methane (≤10.4 mg/L). Between one and fourteen PFAS were detected at all sites and PFOS, PFHxS, PFOA and PFBS were detected in all samples. The sum of detected PFAS (∑₁₄PFAS) varied from 26 ng/L at an ambient background site to 5,200 ng/L near a potential industrial point-source. PFHxS had the highest median concentration (34 ng/L; range: 2.6–280 ng/L) followed by PFOS (26 ng/L; range: 1.3–4,800 ng/L), PFHxA (19 ng/L; range: <LOQ – 46 ng/L) and PFOA (12 ng/L; range: 1.7–74 ng/L). Positive correlations between ∑₁₄PFAS, PFOA and other perfluoroalkyl carboxylic acids (PFCAs) (e.g. PFHxA) with typical leachate indicators including ammonia-N and bicarbonate were observed. In contrast, no such correlations were found with perfluoroalkyl sulfonic acids (PFSAs) (e.g., PFOS and PFHxS). In addition, a strong positive linear correlation (R² = 0.69) was found between the proportion of PFOA in the sum of detected perfluorinated alkylated acids (PFOA/∑PFAA) and ammonia-N concentrations in groundwater. This is consistent with previous research showing relatively high PFOA/∑PFAA in municipal landfill leachates, and more conservative behaviour (e.g. less sorption and reactivity) of PFCAs during subsurface transport compared to PFSAs. PFOA/∑PFAA in groundwater may therefore be a useful indicator of municipal landfill-derived PFAA. One site with significantly elevated PFOS and PFHxS concentrations (4,800 and 280 ng/L, respectively) appears to be affected by point-source industrial contamination, as landfill leachate indicators were absent.