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.

Surface functionalization and shape modifications are the key strategies being utilized to overcome the limitations of semiconductors in advanced oxidation processes (AOP). Herein, the uniform α-Fe₂O₃ nanocrystals (α-Fe₂O₃–NCs) were effectively synthesized via a simple solvothermal route. Meanwhile, the sulfonic acid functionalization (SAF) and the impregnation of α-Fe₂O₃–NCs on g-C₃N₄ (α-Fe₂O₃–NCs@CN-SAF) were achieved through complete solvent evaporation technique. The surface functionalization of the sulfonic acid group on g-C₃N₄ accelerates the faster migration of electrons to the surface owing to robust electronegativity. The incorporation of α-Fe₂O₃–NCs with CN-SAF significantly enhances the optoelectronic properties, ultrafast spatial charge separation, and rapid charge transportation. The α-Fe₂O₃-HPs@CN-SAF and α-Fe₂O₃-NPs@CN-SAF nanocomposites attained 97.41% and 93.64% of Cr (VI) photoreduction in 10 min, respectively. The photocatalytic efficiency of α-Fe₂O₃–NCs@CN-SAF nanocomposite is 2.4 and 2.1 times higher than that of pure g-C₃N₄ and α-Fe₂O₃, respectively. Besides, the XPS, PEC and recycling experiments confirm the excellent photo-induced charge separation via Z-scheme heterostructure and cyclic stability of α-Fe₂O₃–NCs@CN-SAF nanocomposites.

Rivers can receive the input of treated or untreated sewage effluents from wastewater treatment plants, urban and industrial discharges and agricultural run-off, becoming an important pathway for the transport and mobilization of pollutants to the oceans. In the present study, the occurrence of 20 PFAAs was determined in the water of Tagus River basin (Spain). PFAAs were detected in 76 out of 92 water samples collected during 5 years (2013–2018), being perfluorooctanesulfonic acid (PFOS) the predominant compound (<0.01–34 ng/L). The annual average PFOS concentrations (2.9–11 ng/L) detected in Tagus River were above the annual average environmental quality standards (AA-EQS) established in the Directive, 2013/39/EU (0.65 ng/L for inland surface waters) but below the maximum allowable concentration (MAC-EQS; 36000 ng/L). The levels of PFAAs detected in urban and industrial areas were statistically higher (p < 0.01) than those at background or remote areas. The mass flow rates amounted to <0.01–46 kg/y for PFOS and <0.01–22 kg/y for perfluorooctanoic acid (PFOA). A quantitative ecotoxicological risk assessment was conducted to evaluate the environmental potential risk related to PFAAs in the aquatic ecosystem. Risk characterization ratios (RCRwater, RCRsed and RCRoral, fish) were below 1 in all cases.

Environmental contaminant monitoring traditionally relies on targeted analysis, and very few tools are currently available to monitor “unexpected” or “unknown” compounds. In the present study, a non-targeted workflow (suspect screening) was developed to investigate plastic-related chemicals and other environmental contaminants in a top predator freshwater fish species, the northern pike, from the St. Lawrence River, Canada. Samples were extracted using sonication-assisted liquid extraction and analyzed by high performance liquid chromatography coupled with quadrupole time of flight mass spectrometry (HPLC-QTOF-MS). Ten bisphenol compounds were used to test the analytical performances of the method, and satisfactory results were obtained in terms of instrumental linearity (r2 > 0.97), recoveries, (86.53–119.32%), inter-day precision and method detection limits. The non-targeted workflow data processing parameters were studied, and the peak height filters (peak filtering step) were found to influence significantly the capacity to detect and identify trace chemicals in pike muscle extracts. None of the ten bisphenol analogues were detected in pike extracts suggesting the absence of accumulation for these chemicals in pike muscle. However, the non-targeted workflow enabled the identification of diethyl phthalate (DEP) and perfluorooctanesulfonic acid (PFOS) in pike extracts. This approach thus can be also applied to various contaminants in other biological matrices and environmental samples.

In this work, anthraquinone-2-sulfonate (AQS) was covalently immobilized onto activated carbon cloth (ACC), to be used as redox mediator for the reductive decolorization of reactive red 2 (RR2) by an anaerobic consortium. The immobilization of AQS improved the capacity of ACC to transfer electrons, evidenced by an increment of 3.29-fold in the extent of RR2 decolorization in absence of inhibitors, compared to incubations lacking AQS. Experiments conducted in the presence of vancomycin, an inhibitor of acidogenic bacteria, and with 2-bromoethane sulfonic acid (BES), an inhibitor of methanogenic archaea, revealed that acidogenic bacteria are the main responsible for RR2 biotransformation mediated by immobilized AQS. Nonetheless, the results also suggest that some methanogens are able to maintain their capacity to use immobilized AQS as an electron acceptor to sustain the decolorization process, even in the presence of BES.

The impact of point and diffuse sources for 26 per- and polyfluoroalkyl substances (PFASs) in northern Europe were investigated by studying Swedish rivers (n = 40) and recipient seawater (Baltic Sea and Kattegat; n = 18). Different composition profiles were observed in the rivers, with ten rivers having a remarkably high fraction of perfluoroalkane sulfonic acids (PFSAs; 65% of the ƩPFASs) as compared to other rivers (19%) suggesting major impact of one or several source types dominated by PFSAs. Population density and low latitude (south) were strongly correlated to the widely used perfluorooctanesulfonic acid (PFOS), perfluorooctanoic acid (PFOA) as well as to perfluorohexanesulfonic acid (PFHxS). Significant relationships between several PFCAs and PFSAs (i.e. perfluorobutanoic acid (PFBA), perfluoroheptanoic acid (PFHpA), PFOA, perfluorobutanesulfonic acid (PFBS), and PFHxS) and dissolved organic carbon (DOC) were detected (p < 0.05), indicating chemical binding and co-transport with DOC in fresh water and seawater. Partial least squares regression analysis showed that perfluoroalkyl carboxylic acids (PFCAs) were related to latitude according to their perfluorocarbon chain length (C3, C7, C8, C9, C10 and C11), with longer chains associated with higher latitudes. This suggests the presence of mechanisms promoting higher prevalence of longer chained PFCAs in the north, e.g. precursor degradation, and/or aerosol associated stabilization of PFCAs and their precursors.