Accumulation, biodegradation and toxicological effects of N-ethyl perfluorooctane sulfonamidoethanol on the earthworms Eisenia fetida exposed to quartz sands.

While N-ethyl perfluorooctane sulfonamidoethanol (EtFOSE) is a precursor of perfluorooctane sulfonate (PFOS), its bioaccumulation, transformation and toxicological effects in earthworms (Eisenia fetida) exposed to quartz sands are poorly understood. The present study showed that except for parent EtFOSE, N-ethylperfluorooctane sulfonamide acetate (EtFOSAA), N-ethyl perfluorooctane sulfonamide (EtFOSA), perfluorooctane sulfonamide acetate (FOSAA), perfluorooctane sulfonamide (FOSA) and PFOS were detected in earthworms, with EtFOSAA as the primary biotransformation product. The biota-to-sand accumulation factor (BSAF) and uptake rate coefficient (ku) of EtFOSE were 5.7 and 0.542/d, respectively. The elimination rate constants (ke) decreased in the order EtFOSA (0.167/d) ∼ FOSAA (0.147/d) > FOSA (0.119/d) ∼ EtFOSAA (0.117/d) > EtFOSE (0.095/d) > PFOS (0.069/d). No significant effects were observed in malondialdehyde (MDA) contents and acetylcholinesterase (AChE) activities between EtFOSE treatments and controls. EtFOSE could cause significant accumulation of reactive oxygen species (ROS) in earthworms. Peroxidase (POD), superoxide dismutase (SOD) and catalase (CAT) were significantly activated by 41.4-74.3%, 37.2-44.4% and 32.4-52.3% from day 4-10, respectively, while 8-Hydroxy-2-deoxyguanosine (8-OHdG) levels were elevated by 47.7-70.3% from day 8-10, demonstrating that EtFOSE induced oxidative stress and oxidative DNA damage in earthworms. Significant increase of glutathione-S-transferase (GST) with 41.6-62.8% activation (8-10 d) gave indirect evidence on the conjugation of EtFOSE or its corresponding metabolites during phase II of detoxication. This study provides important information on the fate and potential risks of EtFOSE to terrestrial invertebrates.

Biotransformation and responses of antioxidant enzymes in hydroponically cultured soybean and pumpkin exposed to perfluorooctane sulfonamide (FOSA).

Perfluorooctane sulfonamide (FOSA) is an important perfluorooctane sulfonate (PFOS) precursor used for commercial applications. In order to investigate the transformation and responses of selected antioxidant and degradation enzymes of FOSA in the plants, in vivo exposure of soybean (Glycine max L. Merrill) and pumpkin (Cucurbita maxima L.) were conducted in the solution-plant microcosms. FOSA was readily taken up by soybean and pumpkin roots and translocated to shoots, and metabolized to PFOS, perfluorohexane sulfonate (PFHxS) and perfluorobutane sulfonate (PFBS). Although morphological and biomass effects were not visible, significant changes in oxidative stress response were observed except for thiobarbituric acid reactive substances (TBARS). Superoxide dismutase (SOD) and peroxidase (POD) activities were significantly increased by 19.2-30.8% and 19.2-20.7% in soybean (8-12 d) respectively, and increased by 39.2-92.8% and 21.1-37.6% in pumpkin (3-12 d) respectively, suggesting an activation of the antioxidant defense system in the plants exposed to FOSA. Glutathione-S-transferase (GST) activities were decreased in soybean (2-12 d) with 9.0-36.1% inhibition and increased in pumpkin (3-12 d) with 22.5-47.3% activation respectively; cytochrome P450 (CYP450) activities were increased markedly in soybean and pumpkin with 13.2-53.6% and 26.7-50.2% activation respectively, giving indirect evidences on the involvement of CYP450 and GST in degradation of FOSA in plants.

Contributions of enzymes and gut microbes to biotransformation of perfluorooctane sulfonamide in earthworms (Eisenia fetida).

Perfluorooctane sulfonamide (FOSA) is known as a key intermediate of perfluorooctane sulfonic acid (PFOS) precursors, which can be frequently detected in the environment and biota. FOSA could be bioaccumulated in earthworms from soil, but the contributions of enzymes and gut microbes involved in the biotransformation of FOSA in earthworms have not been identified. Therefore, the effects of enzyme inhibitors and intestinal microflora on biotransformation of FOSA in earthworms were investigated in the present study. FOSA was biotransformed to form PFOS by earthworms obtained from in vivo and in vitro tests. The addition of FOSA had significantly positive effects on cytolchrome P450 (CYP450) and glutathione-s-transferase (GST) activities, suggesting CYP450 and GST are likely involved in the enzymatic transformation. In addition, both 1-Aminobenzotriazole (ABT) and ezatiostat hydrochloride (TLK199), which were selected to inhibit the CYP and GST enzymes, respectively, demonstrated inhibition effects on biotransformation of FOSA in earthworms with a dose-dependent relationship. However, the concentrations of FOSA weren't changed by the bacteria isolated from worm gut, suggesting that gut bacteria did not contribute to FOSA biotransformation in earthworms. The results of this study confirm that the transformation of FOSA in earthworms is mediated mainly by enzymes rather than by gut microbes.

Fate of 6:2 fluorotelomer sulfonic acid in pumpkin (Cucurbita maxima L.) based on hydroponic culture: Uptake, translocation and biotransformation.

6:2 fluorotelomer sulfonic acid (6:2 FTSA) is currently used as an alternative to perfluorooctanesulfonate (PFOS) and is widely detected in the environment. The uptake, translocation and biotransformation of 6:2 FTSA in pumpkin (Cucurbita maxima L.) were investigated by hydroponic exposure for the first time. The root concentration factor (RCF) of 6:2 FTSA was 2.6-24.2 times as high as those of perfluoroalkyl acids (PFAAs) of the same or much shorter carbon chain length, demonstrating much higher bioaccumulative ability of 6:2 FTSA in pumpkin roots. The translocation capability of 6:2 FTSA from root to shoot depended on its hydrophobicity. Six terminal perfluorocarboxylic acid (PFCA) metabolites, including perfluoroheptanoic acid (PFHpA), perfluorohexanoic acid (PFHxA), perfluoropentanoic acid (PFPeA), perfluorobutanoic acid (PFBA), perfluoropropionic acid (PFPrA) and trifluoroacetic acid (TFA) were found in pumpkin roots and shoots. PFHpA was the primary metabolite in roots, while PFBA was the major product in shoots. 1-aminobenzotriazole (ABT), a cytochromes P450 (CYPs) suicide inhibitor, could decrease the concentrations of PFCA products with dose-dependent relationships in pumpkin tissues, implying the role of CYP enzymes involved in plant biotransformation of 6:2 FTSA. This study indicated that the application of 6:2 FTSA can lead to the occurrence of PFCAs (C2-C7) in plants.

[Isolation, Identification, and Biodegradation Behaviors of a Perfluorooctane Sulfonic Acid Precursor (PreFOSs) Degrading Bacterium from Contaminated Soil].

Transformation of perfluorooctane sulfonate (PFOS) precursors (PreFOSs) is considered an additional source of PFOS in the environment and biota. A PreFOSs-degrading bacterium PF1, which was able to utilize PreFOSs as the sole carbon and energy source for growth, was isolated from contaminated soil collected from the surroundings of a fluoride factory. According to its morphology and 16S rDNA gene sequence analysis, strain PF1 was identified as Hyphomicrobium sp. The degradation rates of perfluorooctane sulfonamide (PFOSA) and N-ethyl perfluorooctane sulfonamide (N-EtFOSA) by PF1 were 14.6% and 8.2% (30℃; pH=7.0-7.2), respectively, whereas PF1 was unable to degrade PFOS. PFOSA could be biodegraded to PFOS. N-EtFOSA could be biodegraded to perfluorooctane sulfonamide acetic acid (FOSAA), PFOSA, and PFOS; PFOS was the predominant metabolite. Based on the above analysis, the proposed metabolic pathway of PFOSA by strain PF1 is deamination to form PFOS. Two possible degradation pathways are proposed for N-EtFOSA: ① deethylation of N-EtFOSA to produce PFOSA, followed by deamination to form PFOS, and ②oxidation of N-EtFOSA to FOSAA followed by sequential dealkylation to produce PFOSA, and then transformation to PFOS by deamination.

Uptake, elimination and biotransformation of N-ethyl perfluorooctane sulfonamide (N-EtFOSA) by the earthworms (Eisenia fetida) after in vivo and in vitro exposure.

N-ethyl perfluorooctane sulfonamide (N-EtFOSA) is commonly known as the active ingredient of sulfluramid. It can be degraded to perfluorooctane sulfonic acid (PFOS) in biota and environment. Earthworms (Eisenia fetida) were exposed with N-EtFOSA to examine the bioaccumulation, elimination and metabolism of N-EtFOSA by the earthworms after in vivo and in vitro exposure. N-EtFOSA could be biodegraded in quartz sands to perfluorooctane sulfonamide (FOSA) and PFOS. In the in vivo tests, in addition to parent N-EtFOSA, three metabolites, including perfluorooctane sulfonamide acetate (FOSAA), FOSA and PFOS also accumulated in earthworms as a result of N-EtFOSA biotransformation, with FOSA as the predominant metabolite. The bioaccumulation factor (BAF) and uptake rate coefficient (ku) of N-EtFOSA from sand were 20.4 and 2.41·d-1, respectively. The elimination rate constants (ke) decreased in the order FOSAA (0.130·d-1) > N-EtFOSA (0.118·d-1) > FOSA (0.073·d-1) > PFOS (0.051·d-1). The biotransformation of N-EtFOSA in earthworm was further confirmed by the in vitro test involving incubation of earthworm homogenates with N-EtFOSA. This work provides evidence on the accumulation and transformation of N-EtFOSA in terrestrial invertebrates and will be helpful to explore the indirect sources of FOSA and PFOS in environmental biota.