Direct emissions from fluorochemical manufactory are an important source of per- and polyfluoroalkyl substances (PFASs) to the environment. In this study, a wide range of PFASs, including 8 legacy PFASs, 8 long-chain perfluoroalkyl carboxylic acids (PFCAs), and 40 emerging PFASs, were investigated through a target screening in multienvironmental matrices from a fluorochemical manufactory in China. Indoor dust was the most polluted matrix, wherein 52 PFASs were detected, and the median concentration of long-chain PFCA was 276 ng/g. A high level of short-chain PFAS in total suspended particles (median concentration = 416 ng/m3) and the effluent in the manufactory (Σ48PFAS = 212 μg/L) will undoubtedly increase the burden on the surrounding environment. Twenty-four industrial byproducts were ascertained to be generated during the electrochemical fluorination (ECF) process, and eight fluorinated alternatives were considered to be produced during product development. Twelve PFASs were quantified for the first time in the working environments. Perfluoropropane sulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid (PFEESA), and 2-perfluorohexyl ethanoic acid are abundant fluorinated alternatives, with median levels of 1187-17204 ng/g in the dust. Significant positive correlations between ECF-related PFAS products and byproducts indicate that the detected values are strongly connected with the industrial source. Hierarchical cluster analysis further manifests their affiliation. Our findings raise the need for further investigations of emerging PFAS (including the first report of PFAS, such as PFEESA, in the environment) which may be released during the production process in the fluorochemical manufactories.

Vital Environmental Sources for Multitudinous Fluorinated Chemicals: New Evidence from Industrial Byproducts in Multienvironmental Matrices in a Fluorochemical Manufactory.

Comparison of developmental toxicity induced by PFOA, HFPO-DA, and HFPO-TA in zebrafish embryos.

The objectives of this study were to identify both legacy and emerging per- and polyfluoroalkyl substances (PFAS) from three typical fluoridated industrial parks (FIPs) in China, and to assess their environmental occurrence and fate. Complementary suspect target and nontarget screening were implemented, and a total of 111 emerging PFAS were identified. Based on the multi-mass scale analysis, 25 emerging PFAS were identified for the first time, including 24 per- and polyfluoroalkyl ether carboxylic acids (PFECAs) and 1 ultra-short chlorinated perfluoroalkyl carboxylic acids (Cl-PFCAs, C2), with a maximum percentage of 48.2 % in nontarget PFAS (exclude target PFAS). The composition of PFAS identified in different media was influenced by functional groups, carbon chain length, substituents and ether bond insertion, with poly-hydrogen substituted being preferably in water and a more diverse pattern of PFECAs in sediments. The patterns of PFAS homologs revealed distinct differences among the three typical FIPs in the shift of PFAS production patterns. The C4-PFAS and short-chain carboxylic acids (≤C6) were the main PFAS in the Fuxin and Changshu, respectively. In contrast, perfluorooctanoic acid (PFOA, C8) remained dominant in Zibo, and the highest point concentrations in water and sediment were up to 706 µg/L and 553 µg/g, respectively.

Target and nontarget analysis of per- and polyfluoroalkyl substances in surface water, groundwater and sediments of three typical fluorochemical industrial parks in China.

Comprehensive profiles of per- and polyfluoroalkyl substances in Chinese and African municipal wastewater treatment plants: New implications for removal efficiency

Oil refinery activity can be an emission source of perfluoroalkyl and polyfluoroalkyl substances (PFAS) to the environment, while the contamination profiles in soils remain unknown. This study investigated 44 target PFAS in soil samples collected from an oil refinery in Southeastern China, identified novel PFAS, and characterized their behaviors by assessing their changes before and after employing advanced oxidation using a combination of nontarget analysis and a total oxidizable precursor (TOP) assay. Thirty-four target PFAS were detected in soil samples. Trifluoroacetic acid (TFA) and hexafluoropropylene oxide dimer acid (HFPO-DA) were the dominant PFAS. Twenty-three novel PFAS of 14 classes were identified, including 8 precursors, 11 products, and 4 stable PFAS characterized by the TOP assay. Particularly, three per-/polyfluorinated alcohols were identified for the first time, and hexafluoroisopropanol (HFIP) quantified up to 657 ng/g dw is a novel precursor for TFA. Bistriflimide (NTf2) potentially associated with an oil refinery was also reported for the first time in the soil samples. This study highlighted the advantage of embedding the TOP assay in nontarget analysis to reveal not only the presence of unknown PFAS but also their roles in environmental processes. Overall, this approach provides an efficient way to uncover contamination profiles of PFAS especially in source-impacted areas.

Nontarget Identification of Novel Per- and Polyfluoroalkyl Substances (PFAS) in Soils from an Oil Refinery in Southwestern China: A Combined Approach with TOP Assay.

Various per- and polyfluoroalkyl substances (PFASs) remain undiscovered and unexplored in the environment. The goals of this study were to discover new species of PFASs in effluent and surface waters from a fluorochemical industrial zone, and to assess their concentration, distribution, and temporal trends in the adjacent natural environment. In total, 83 emerging PFASs from 14 classes were identified, 22 of which were reported for the first time. Authentic standards were synthesized for 13 per- and polyfluoroalkyl ether carboxylic acids (PFECAs), thereby greatly expanding the scope of PFAS-targeted monitoring. The newly identified compounds accounted for 27%–95% of the total PFAS concentrations. Of note, a novel diether carboxylic acid, 2-[2-(trifluoromethoxy)hexafluoropropoxy]tetrafluoropropanoic acid (C7 HFPO-TA) was detected at an extremely high concentration in the fluorochemical zone effluent (447 000 ng/L) and at a median concentration in the fluorochemical zone surface water (670 ng/L), with detectable levels also found in the natural environment, that is, Wangyu River (23 ng/L) and Taihu Lake (5.6 ng/L). The distinct geographic distribution of C7 HFPO-TA suggests transport from the industrial point source to Taihu Lake via the Wangyu River. The concentration of C7 HFPO-TA in Taihu Lake, along with that of many other emerging PFASs, continued to grow in three sampling campaigns from 2016 to 2021. Considering the environmental persistence and toxicity of structurally similar PFECAs (e.g., HFPO–DA), studies on C7 HFPO-TA are urgently needed. 

Nontargeted Identification and Temporal Trends of Per- and Polyfluoroalkyl Substances in a Fluorochemical Industrial Zone and Adjacent Taihu Lake

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Nontargeted Identification and Temporal Trends of Per- and Polyfluoroalkyl Substances in a Fluorochemical Industrial Zone and Adjacent Taihu Lake

Comprehensive profiles of per- and polyfluoroalkyl substances in Chinese and African municipal wastewater treatment plants: New implications for removal efficiency