The ubiquitous occurrence of per- and polyfluoroalkyl substances (PFAS) and the detection of unexplained extractable organofluorine (EOF) in drinking water have raised growing concerns. A recent study reported the detection of inorganic fluorinated anions in German river systems, and therefore, in some samples, EOF may include some inorganic fluorinated anions. Thus, it might be more appropriate to use the term "extractable fluorine (EF) analysis" instead of the term EOF analysis. In this study, tap water samples (n = 39) from Shanghai were collected to assess the levels of EF/EOF, 35 target PFAS, two inorganic fluorinated anions (tetrafluoroborate (BF4-) and hexafluorophosphate (PF6-)), and novel PFAS through suspect screening and potential oxidizable precursors through oxidative conversion. The results showed that ultra-short PFAS were the largest contributors to target PFAS, accounting for up to 97% of ΣPFAS. To the best of our knowledge, this was the first time that bis(trifluoromethanesulfonyl)imide (NTf2) was reported in drinking water from China, and p-perfluorous nonenoxybenzenesulfonate (OBS) was also identified through suspect screening. Small amounts of precursors that can be oxidatively converted to PFCAs were noted after oxidative conversion. EF mass balance analysis revealed that target PFAS could only explain less than 36% of EF. However, the amounts of unexplained extractable fluorine were greatly reduced when BF4- and PF6- were included. These compounds further explained more than 44% of the EF, indicating the role of inorganic fluorinated anions in the mass balance analysis.
17 January 2022 in Science of The Total Environment
The environmental and human health concerns for organohalogen contaminants (OHCs) extend beyond the 23 persistent organic pollutants (POPs) regulated by the Stockholm Convention. The current, intense industrial production and use of chemicals in China and their bioaccumulation makes Chinese wildlife highly suitable for the assessment of legacy, novel and emerging environmental pollutants. In the present study, six species of amphibians, fish and birds were sampled from paddy fields in the Yangtze River Delta (YRD) were screened for OHCs. Some extensive contamination was found, both regarding number and concentrations of the analytes, among the species assessed. High concentrations of chlorinated paraffins were found in the snake, Short-tailed mamushi (range of 200-340 μg g(-)(1)lw), Peregrine falcon (8-59 μg g(-1)lw) and Asiatic toad (97 μg g(-)(1)lw). Novel contaminants and patterns were observed; octaCBs to decaCB made up 20% of the total polychlorinated biphenyls (PCBs) content in the samples and new OHCs, substituted with 5-8 chlorines, were found but are not yet structurally confirmed. In addition, Dechlorane 602 (DDC-DBF) and numerous other OHCs (DDTs, hexachlorocyclohexanes (HCHs), polybrominated diphenyl ethers (PBDEs), hexbromocyclododecane (HBCDD), chlordane, heptachlor, endosulfan and Mirex) were found in all species analyzed. These data show extensive chemical contamination of wildlife in the YRD with a suite of OHCs with both known and unknown toxicities, calling for further in-depth studies.
In this study, polybrominated diphenyl ethers (PBDEs) and methoxylated polybrominated diphenyl ethers (MeO-PBDEs) were analyzed in eleven freshwater fish species from Dianshan Lake, Shanghai, China. The highest concentrations of PBDEs and MeO-PBDEs were found in snakehead, with mean values of 38 ng g-1 lw and 4.2 ng g-1 lw, respectively. BDE-47 was the predominant congener of PBDEs, followed by BDE-154. Congener pattern variation of PBDEs was observed among different fish species, implying differences in biotransformation potential among fish. Yellow catfish showed highest concentrations of BDE-99, -153 and -183, suggesting that it is more resistant to debromination than any other fish analyzed in the present study. Trophic magnification factors were in the range of 1.35-1.81 for all the PBDE congeners, but not for 2'-MeO-BDE-68. Negative relationship was observed between PBDEs concentration and sample size (length and weight), indicating fish size dilution effect.
Alkyl organophosphate flame retardants (OPFRs), tri-n-butyl phosphate (TnBP) and tris(2-butoxyethyl) phosphate (TBOEP), are ubiquitously detected in indoor and outdoor environments and their inhalation may result in lung damage. This study examined pulmonary toxicity after exposure to TnBP or TBOEP and investigated aggravation of inflammation and immunoreaction by TnBP in an ovalbumin (OVA)-induced mice model. Transcriptomics were used to further reveal the underlying mechanism. Exposure to TnBP or TBOEP resulted in pathological damage, including edema and thickened alveolar septum. In comparison with the control, enhanced levels of superoxide dismutase (SOD) (p < 0.01 in TnBP (High) group and p < 0.05 in TBOEP (High) group), glutathione peroxidase (GSH-px) (p < 0.05), malondialdehyde (MDA) (p < 0.01), and cytokines under a dose-dependent relationship were noted, and the expression of the Fkbp5/Nos3/MAPK/NF-кB signaling pathway (p < 0.01) was upregulated in the TnBP and TBOEP groups. Moreover, the combined exposure of TnBP and OVA exacerbated the allergic inflammatory response, including airway hyperresponsiveness, leukocytosis, cellular exudation and infiltration, secretion of inflammatory mediators, and higher expression of IgE (p < 0.01). Transcriptomics results demonstrated that the PI3K/Akt/NF-кB signal pathway was involved in TnBP-aggravated asthmatic mice. Exposure to TnBP or TBOEP resulted in oxidative damage and leukocyte-induced lung injury. TnBP can further facilitate OVA-induced asthma through an inflammatory response. This study is the first to reveal the pulmonary toxicity and potential mechanism induced by OPFRs through an in-vivo model.