Warming Affects Bioconcentration and Bioaccumulation of Per- and Polyfluoroalkyl Substances by Pelagic and Benthic Organisms in a Water-Sediment System.

Warming and exposure to emerging global pollutants, such as per- and polyfluoroalkyl substances (PFAS), are significant stressors in the aquatic ecosystem. However, little is known about the warming effect on the bioaccumulation of PFAS in aquatic organisms. In this study, the pelagic organisms Daphnia magna and zebrafish, and the benthic organism Chironomus plumosus were exposed to 13 PFAS in a sediment-water system with a known amount of each PFAS at different temperatures (16, 20, and 24 °C). The results showed that the steady-state body burden (Cb-ss) of PFAS in pelagic organisms increased with increasing temperatures, mainly attributed to increased water concentrations. The uptake rate constant (ku) and elimination rate constant (ke) in pelagic organisms increased with increasing temperature. In contrast, warming did not significantly change or even mitigate Cb-ss of PFAS in the benthic organism Chironomus plumosus, except for PFPeA and PFHpA, which was consistent with declined sediment concentrations. The mitigation could be explained by the decreased bioaccumulation factor due to a more significant percent increase in ke than ku, especially for long-chain PFAS. This study suggests that the warming effect on the PFAS concentration varies among different media, which should be considered for their ecological risk assessment under climate change.

Fractionation of perfluoroalkyl acids (PFAAs) along the aquatic food chain promoted by competitive effects between longer and shorter chain PFAAs.

Perfluoroalkyl acids (PFAAs) are proteinophilic pollutants. We hypothesized that fractionation of PFAAs may occur along a food chain. To testify this hypothesis, we investigated the bioconcentration, bioaccumulation, and fractionation of 11 kinds of PFAAs (C-F = 3-11) along an aquatic food chain consisting of D. magna, zebrafish, and cichlid. The results showed that the proportions of PFNA, PFOA, and all shorter chain PFAAs in the D. magna and fish tissues were lower than the ones in exposure water, opposing to the other longer chain PFAAs. Predation promoted such fractionation differences, and the proportions of PFNA, PFOA, and all shorter chain PFAAs in organisms decreased while those of the other longer chain PFAAs increased along the food chain. The results of isothermal titration calorimetry and molecular docking experiments showed that binding affinities of PFAAs and fish proteins increased with the number of perfluorinated carbons, resulting in a substitution of shorter chain PFAAs by their longer chain analogues. It also triggered the differences in the uptake and elimination of PFFAs and competitive bioaccumulation between longer and shorter chain PFAAs. This study suggests that fractionation should be considered in studying environmental behaviors and evaluating ecological risks of multiple PFAAs.

An unexpected synergistic toxicity caused by competitive bioconcentration of perfluoroalkyl acid mixtures to Daphnia magna: Further promoted by elevated temperature.

The mixed pollution of the global water environment by perfluoroalkyl acids (PFAAs) and their ecological risks have aroused widespread concern. However, the relationship between the combined toxicity of PFAA mixtures and their accumulation in aquatic organisms is not well understood in the context of global warming. Here, we study the bioconcentration and combined toxicity of three PFAA mixtures (PFOA, PFDA, PFDoA) to Daphnia magna (D. magna) under different exposure concentrations and temperatures. The results show that although competitive bioconcentration exists, the combined toxicity of the PFAA mixtures to D. magna is synergistic. These contradictory phenomena occur because although the longer-chain PFDoA inhibits the bioconcentration of the shorter-chain PFOA and PFDA, the bioconcentration of PFDoA itself is promoted, and PFDoA is more toxic to D. magna than PFOA and PFDA. The toxic equivalent concentration for the PFAA mixture is 1.38-1.67 times higher than that obtained from simple addition for the three PFAAs when exposed separately. Moreover, elevated temperature promotes not only the bioconcentration of each PFAA and the competition of bioconcentration between shorter-chain and longer-chain PAFF, but also the synergistic toxicity of PFAA mixtures to D. magna. This study suggests that the effect of the interactions among different PFAAs on their bioconcentration and toxicity under different water environmental conditions, such as temperature, should be considered for ecological risk assessment of PFAA mixtures.

Bioconcentration and tissue distribution of shorter and longer chain perfluoroalkyl acids (PFAAs) in zebrafish (Danio rerio): Effects of perfluorinated carbon chain length and zebrafish protein content.

Perfluoroalkyl acids (PFAAs) are a class of emerging pollutants. However, the bioconcentration and tissue distribution of shorter chain PFAAs in aquatic animals are not well understood. Here, we investigated the effects of perfluorinated carbon chain length of PFAAs and protein content of tissues on the bioconcentration and tissue distribution of both shorter chain PFAAs (linear C-F = 3-6) and longer chain PFAAs (linear C-F = 7-11) in zebrafish. The results showed that the uptake rate constants (ku) and the bioconcentration factors (BCFss) of the shorter chain PFAAs (0.042-32 L·kgww-1·d-1 and 0.12-24 L·kgww-1, respectively) in tissues were significantly lower than those of the longer chain PFAAs (2.8-1.4 × 103 L·kgww-1·d-1 and 9.7-1.9 × 104 L·kgww-1, respectively). Moreover, the concentrations of both longer and shorter chain PFAAs were lowest in the muscle where the protein content was lowest, and they were highest in blood and liver where the protein content was highest among tissues except brain. The protein content of the brain was higher than that of the liver but the concentrations of PFAAs in the brain were significantly lower than those in the liver because of the blood-brain barrier. In addition, the ovary/blood and brain/blood ratios of concentrations for the shorter chain PFAAs were lower than those for the longer chain PFAAs. Generally, both log ku and log BCFss showed a significantly positive correlation with either perfluorinated carbon number of PFAAs or protein content of tissues (P < 0.05). Further nonlinear surface fitting revealed that the effect of perfluorinated carbon number was more significant than protein content on the PFAA bioconcentration in zebrafish tissues. These results suggest that there are differences in the bioconcentration and tissue distribution between longer and shorter chain PFAAs and the shorter chain PFAAs seem to be safe compared with the longer chain PFAAs.

Long-Chain Perfluoroalkyl acids (PFAAs) Affect the Bioconcentration and Tissue Distribution of Short-Chain PFAAs in Zebrafish (Danio rerio).

Short- and long-chain perfluoroalkyl acids (PFAAs), ubiquitously coexisting in the environment, can be accumulated in organisms by binding with proteins and their binding affinities generally increase with their chain length. Therefore, we hypothesized that long-chain PFAAs will affect the bioconcentration of short-chain PFAAs in organisms. To testify this hypothesis, the bioconcentration and tissue distribution of five short-chain PFAAs (linear C-F = 3-6) were investigated in zebrafish in the absence and presence of six long-chain PFAAs (linear C-F = 7-11). The results showed that the concentrations of the short-chain PFAAs in zebrafish tissues increased with exposure time until steady states reached in the absence of long-chain PFAAs. However, in the presence of long-chain PFAAs, these short-chain PFAAs in tissues increased until peak values reached and then decreased until steady states, and the uptake and elimination rate constants of short-chain PFAAs declined in all tissues and their BCFss decreased by 24-89%. The inhibitive effect of long-chain PFAAs may be attributed to their competition for transporters and binding sites of proteins in zebrafish with short-chain PFAAs. These results suggest that the effect of long-chain PFAAs on the bioconcentration of short-chain PFAAs should be taken into account in assessing the ecological and environmental effects of short-chain PFAAs.