Aqueous film-forming foams (AFFFs) are widely used to extinguish liquid fires due to their film-forming properties. AFFF formulation historically contains per- and polyfluoroalkyl substances (PFASs) ...that can be very persistent and pose a health risk to biota and humans. Detailed analysis of the chemical composition of AFFFs can provide a better understanding on the potential environmental impact of the ingredients. In this study, a novel workflow combining target analysis, nontarget screening analysis (NTA), total fluorine (TF) analysis, and inorganic fluoride (IF) analysis was applied to disclose the chemical composition of 24 foams intended for liquid fires. Foams marketed as containing PFASs as well as fluorine-free foams were included. By comparing the sum of targeted PFASs and total organofluorine concentrations, a mass balance of known and unknown organofluorine could be calculated. Known organofluorine accounted for <1% in most fluorine-containing AFFFs, and it was confirmed that the foams marketed as fluorine-free did not contain measurable amounts of organofluorine substances. Five fluorinated substances were tentatively identified, and non-fluorinated zwitterionic betaine compounds, which are considered to be replacement substances for PFASs, were tentatively identified in the organofluorine-free foams.
Per- and polyfluoroalkyl substances (PFASs) may cross the placental barrier and lead to fetal exposure. However, little is known about the factors that influence maternal-fetal transfer of these ...chemicals. PFAS concentrations were analyzed in 100 paired samples of human maternal sera collected in each trimester and cord sera at delivery; these samples were collected in Wuhan, China, 2014. Linear regression was used to estimate associations of transfer efficiencies with factors. Chlorinated polyfluorinated ether sulfonates (Cl-PFAESs, 6:2 and 8:2) were frequently detected (>99%) in maternal and cord sera. A significant decline in PFAS levels during the three trimesters was observed. A U-shape trend for transfer efficiency with increasing chain length was observed for both carboxylates and sulfonates. Higher transfer efficiencies of PFASs were associated with advancing maternal age, higher education, and lower glomerular filtration rate (GFR). Cord serum albumin was a positive factors for higher transfer efficiency (increased 1.1–4.1% per 1g/L albumin), whereas maternal serum albumin tended to reduce transfer efficiency (decreased 2.4–4.3% per 1g/L albumin). Our results suggest that exposure to Cl-PFAESs may be widespread in China. The transfer efficiencies among different PFASs were structure-dependent. Physiological factors (e.g., GFR and serum albumin) were observed for the first time to play critical roles in PFAS placental transfer.
Data presenting the environmental occurrence of ultra-short-chain perfluoroalkyl acids (PFAAs) are scarce and little is known about the potential sources. In this study, ultra-short-chain PFAAs were ...analyzed in water connected to potential point sources using supercritical fluid chromatography coupled with tandem mass spectrometry. Samples (n = 34) were collected in connection with firefighting training sites, landfills, and a hazardous waste management facility. Ultra-short-chain PFAAs were detected in all samples at concentrations up to 84 000 ng/L (∑C1–C3), representing up to 69% of the concentration of 29 per- and polyfluoroalkyl substances (PFASs). Trifluoroacetic acid (TFA), perfluoropropanoic acid (PFPrA), trifluoromethane sulfonic acid (TFMS), perfluoroethane sulfonic acid (PFEtS), and perfluoropropane sulfonic acid (PFPrS) were detected at concentrations up to 14 000, 53 000, 940, 1700, and 15 000 ng/L, respectively. Principal component analysis suggests that TFA is associated with landfills. PFPrS was associated with samples collected close to the source at all types of sites included in this study. These findings reveal the presence of high concentrations of ultra-short-chain PFAAs released into the environment from various sources and emphasize the large fraction of ultra-short-chain PFAAs to the total concentration of PFASs in water.
Here, we report on the occurrence of a novel perfluoroalkyl ether carboxylic acid, ammonium perfluoro-2-(propoxy)propoxy-1-propanoate (HFPO-TA), in surface water and common carp (Cyprinus carpio) ...collected from the Xiaoqing River and in residents residing near a fluoropolymer production plant in Huantai County, China. Compared with the levels upstream of the Xiaoqing River, HFPO-TA concentrations (5200–68500 ng/L) were approximately 120–1600-times higher downstream after receiving fluoropolymer plant effluent from a tributary. The riverine discharge of HFPO-TA was estimated to be 4.6 t/yr, accounting for 22% of total PFAS discharge. In the wild common carp collected downstream from the point source, HFPO-TA was detected in the blood (median: 1510 ng/mL), liver (587 ng/g ww), and muscle (118 ng/g ww). The log BCFblood of HFPO-TA (2.18) was significantly higher than that of PFOA (1.93). Detectable levels of HFPO-TA were also found in the sera of residents (median: 2.93 ng/mL). This is the first report on the environmental occurrence and bioaccumulation of this novel chemical. Our results indicate an emerging usage of HFPO-TA in the fluoropolymer manufacturing industry and raise concerns about the toxicity and potential health risks of HFPO-TA to aquatic organisms and humans.
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)hexafluoropropoxytetrafluoropropanoic 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.
Concentrations of nine antibiotics erythromycin-H
2O (ERY-H
2O); trimethoprim (TMP); tetracycline (TET); norfloxacin (NOR); penicillin G (PEN G); penicillin V (PEN V); cefalexin (CLX); cefotaxim ...(CTX); and cefazolin (CFZ) were measured in influent and effluent samples from four sewage treatment plants (STPs) in Hong Kong as well as in influent samples from one STP in Shenzhen. Levels of PEN V and CFZ were below method detection limits in all of the samples analyzed. CLX concentrations were the highest in most of the Hong Kong samples, ranging from 670 to 2900
ng/L and 240 to 1800
ng/L in influent and effluent samples, respectively, but CLX was not detected in the samples from Shenzhen. Comparatively lower concentrations were observed for ERY-H
2O (470–810
ng/L) and TET (96–1300
ng/L) in the influent samples from all STPs in Hong Kong. CTX was found to be the dominant antibiotic in the Shenzhen STP influents with a mean concentration of 1100
ng/L, but occurred at lower concentrations in Hong Kong sewage. These results likely reflect regional variations in the prescription and use patterns of antibiotics between Hong Kong and Shenzhen. Antibiotic removal efficiencies depended on their chemical properties and the wastewater treatment processes used. In general, relatively higher removal efficiencies were observed for NOR (5–78%) and TET (7–73%), which are readily adsorbed to particulate matter, while lower removal efficiencies were observed for ERY-H
2O (9–19%), which is relatively persistent in the environment. Antibiotics were removed more efficiently at Hong Kong STPs employing secondary treatment processes compared with those using primary treatment only. Concentrations of NOR measured in effluents from STPs in Hong Kong were lower than the predicted no-effect concentration of 8000
ng/L determined in a previous study. Therefore, concentrations of antibiotics measured in this preliminary study would be unlikely to cause adverse effects on microorganisms used in wastewater treatment processes at the sampled STPs.
The occurrence of per- and polyfluoroalkyl substances (PFASs) in aquatic ecosystems is a global concern because of their persistence, potential bioaccumulation, and toxicity. In this study, we ...investigated a PFAS-contaminated pond in Sweden to assess the cross-boundary transfer of PFASs from the aquatic environment to the riparian zone via emergent aquatic insects. Aquatic and terrestrial invertebrates, surface water, sediments, soils, and plants were analyzed for 24 PFASs including branched isomers. Stable isotope analysis of carbon and nitrogen was performed to elucidate the importance of diet and trophic position for PFAS uptake. We present the first evidence that PFASs can propagate to the riparian food web via aquatic emergent insects. Elevated Σ24PFAS concentrations were found in aquatic insect larvae, such as dragon- and damselflies, ranging from 1100 to 4600 ng g–1 dry weight (dw), and remained high in emerged adults (120–3500 ng g–1 dw), indicating exposure risks for top predators that prey in riparian zones. In terrestrial invertebrate consumers, PFAS concentrations increased with the degree of aquatic-based diet and at higher trophic levels. Furthermore, stable isotope data together with calculated bioaccumulation factors indicated that bioconcentration of PFASs was the major pathway of exposure in the aquatic food web and bioaccumulation in the riparian food web.
This study examined the environmental behaviour and fate of polyfluoroalkyl compounds (PFCs) found in water, suspended particulate matter (SPM) and sediment. The sampling of the sediment was ...performed at two stations from Tokyo Bay, Japan, in 2008. In addition, a depth profile of seawater was collected at three water layers from both sampling stations. The ∑PFC concentrations ranged from 16.7 to 42.3
ng
L
−1 in the water column, from 6.4 to 15.1
ng
g
−1 dry weight (dw) in the SPM fraction and from 0.29 to 0.36
dw in surface sediment. The distribution of PFCs was found to depend on their physicochemical characteristics. While short-chain perfluoroalkyl carboxylic acids (PFCAs) (C
<
7) were exclusively detected in the dissolved phase, longer-chain PFCAs (C
⩾
7), perfluoroalkyl sulfonates (PFSAs), ethylperfluorooctane sulfonamidoacetic acid (EtFOSAA), and perfluorooctane sulfonamide (PFOSA) appeared to bind more strongly to particles. Results showed that the sorption of PFCs on SPM increases by 0.52–0.75 log units for each additional CF
2 moiety and that the sorption of PFSAs was 0.71–0.76 log units higher compared to the PFCA analogs. In addition, the sorption of PFCs was influenced by the organic carbon content. These data are essential for modelling the transport and environmental fate of PFCs.
Studies have highlighted the increasing fraction of unidentified organofluorine (UOF) compounds in human blood, whose health effects are not known. In this study, 130 whole blood samples from the ...Swedish general population were analyzed for extractable organofluorine (EOF) and selected per- and polyfluoroalkyl substances (PFAS). Organofluorine mass balance analysis revealed that 60% (0–99%) of the EOF in female samples could not be explained by the 63 monitored PFAS; in males, 41% (0–93%) of the EOF was of unidentified origin. Significant differences between both age groups and gender were seen, with the highest fraction of UOF in young females (70% UOF, aged 18–44), which is contrary to what has been reported in the literature for commonly monitored compounds (e.g., perfluorooctane sulfonic acid, PFOS). Increasing the number of monitored PFAS did not lead to a large decrease of the UOF fraction; the seven highest PFAS (C8–C11 PFCAs, C6–C8 PFSAs) accounted for 98% of sum 63 PFAS. The high fraction of UOF in human samples is of concern, as the chemical species of these organofluorine compounds remain unknown and thus their potential health risks cannot be assessed.
► The partitioning of PFOA, PFOS and PFOSA between water and sediment was evaluated. ► The log
K
OC was 4.1
cm
3
g
−1 for PFOSA, 3.7
cm
3
g
−1 for PFOS and 2.4
cm
3
g
−1 for PFOA. ► PFOA, PFOS and ...PFOSA were present in the dissolved phase at low SPM concentration. ► The organic content and density of the sediment influencing the partitioning.
Laboratory partitioning experiments were conducted to elucidate the sorption behaviour and partitioning of perfluoroalkyl compounds (PFCs). Three different sediment types were used and separately spiked with perfluorooctanoate (PFOA), perfluorooctane sulfonate (PFOS) and perfluorooctane sulfonamide (PFOSA) at low environmentally realistic concentrations. PFOA, PFOS and PFOSA were mainly distributed in the dissolved phase at low suspended solid concentrations, indicating their long-range transport potential in the marine environment. In all cases, the equilibrium isotherms were linear and the organic carbon normalised partition coefficients (
K
OC) decreased in the following order: PFOSA (log
K
OC
=
4.1
±
0.35
cm
3
g
−1)
>
PFOS (3.7
±
0.56
cm
3
g
−1)
>
PFOA (2.4
±
0.12
cm
3
g
−1). The level of organic content had a significant influence on the partitioning. For the sediment with negligible organic content the density of the sediment became the most important factor influencing the partitioning. Ultimately, data on the partitioning of PFCs between aqueous media and suspended solids are essential for modelling their transport and environmental fate.
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