Quantification of Biodriven Transfer of Per- and Polyfluoroalkyl Substances from the Aquatic to the Terrestrial Environment via Emergent Insects.

Emergent aquatic insects are important food subsidies to riparian food webs but can also transfer waterborne contaminants to the terrestrial environment. This study aimed to quantitatively assess this biodriven transfer for per- and polyfluoroalkyl substances (PFAS). Aquatic insect larvae, emergent aquatic insects, terrestrial consumers, sediment, and water were collected from a contaminated lake and stream and an uncontaminated pond, and analyzed for PFAS and stable isotopes of carbon and nitrogen. Top predators in this study were spiders, which showed the highest average ∑24PFAS concentration of 1400 ± 80 ng g-1 dry weight (dw) at the lake and 630 ng g-1 dw at the stream. The transfer of PFAS from the lake to the riparian zone, via deposition of emergent aquatic insects, was 280 ng ∑24PFAS m-2 d-1 in 2017 and only 23 ng ∑24PFAS m-2 d-1 in 2018. Because of higher production of emergent aquatic insects, the lake had higher PFAS transfer and higher concentrations in terrestrial consumers compared to the stream, despite the stream having higher PFAS concentration in water and aquatic insect larvae. Our results indicate that biodriven transfer of PFAS from the aquatic systems and subsequent uptake in terrestrial food webs depend more on emergence amounts, i.e., aquatic prey availability, rather than on PFAS concentrations in water and aquatic prey.

Per- and Polyfluoroalkyl-Contaminated Freshwater Impacts Adjacent Riparian Food Webs.

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.

Characterization of an AFFF impacted freshwater environment using total fluorine, extractable organofluorine and suspect per- and polyfluoroalkyl substance screening analysis.

The vast number of per- and polyfluoroalkyl substances (PFASs) that are in global commerce (n > 4700) pose immense challenges for environmental monitoring. The large discrepancy between this large number and the few PFASs usually monitored suggest that environmental exposure might be substantially underestimated. This study applied a workflow, which included analysis of total fluorine (TF), extractable organofluorine (EOF), 24 target PFASs and suspect screening. The workflow aimed to close the organofluorine mass balance and to tentatively identify overlooked PFASs in various matrices from an aqueous film forming foam (AFFF) contaminated pond and its adjacent riparian zone. PFAS target analysis revealed that water, aquatic invertebrates as well as emergent aquatic insects had high concentrations with up to 2870 ng L-1, 9230 ng g-1 dry weight (dw) and 1470 ng g-1 dw ∑24PFASs, respectively. The EOF mass balance could be explained by target PFAS analysis for most biota samples such as aquatic invertebrates, emergent aquatic insects and terrestrial spiders and earthworms (i.e. EOF ≈ ∑24PFASs). In the pond surface water, 42-58% of the EOF was not explained by target PFASs. However most new tentatively identified PFASs (n = 25) were detected in water, which could contribute to the unknown EOF. Nine suspects could be further identified, which where perfluoroalkyl sulfonamide-based compounds and derivatives that all have been found in historical AFFFs produced by electrochemical fluorination. One suspect, F5S-PFOS, was also detected for the first time in aquatic and terrestrial invertebrates.

Pharmaceuticals in source separated sanitation systems: Fecal sludge and blackwater treatment.

This study investigated, for the first time, the occurrence and fate of 29 multiple-class pharmaceuticals (PhACs) in two source separated sanitation systems based on: (i) batch experiments for the anaerobic digestion (AD) of fecal sludge under mesophilic (37 °C) and thermophilic (52 °C) conditions, and (ii) a full-scale blackwater treatment plant using wet composting and sanitation with urea addition. Results revealed high concentrations of PhACs in raw fecal sludge and blackwater samples, with concentrations up to hundreds of µg L-1 and µg kg-1 dry weight (dw) in liquid and solid fractions, respectively. For mesophilic and thermophilic treatments in the batch experiments, average PhACs removal rates of 31% and 45%, respectively, were observed. The average removal efficiency was slightly better for the full-scale blackwater treatment, with 49% average removal, and few compounds, such as atenolol, valsartan and hydrochlorothiazide, showed almost complete degradation. In the AD treatments, no significant differences were observed between mesophilic and thermophilic conditions. For the full-scale blackwater treatment, the aerobic wet composting step proved to be the most efficient in PhACs reduction, while urea addition had an almost negligible effect for most PhACs, except for citalopram, venlafaxine, oxazepam, valsartan and atorvastatin, for which minor reductions (on average 25%) were observed. Even though both treatment systems reduced initial PhACs loads considerably, significant PhAC concentrations remained in the treated effluents, indicating that fecal sludge and blackwater fertilizations could be a relevant vector for dissemination of PhACs into agricultural fields and thus the environment.

Point source characterization of per- and polyfluoroalkyl substances (PFASs) and extractable organofluorine (EOF) in freshwater and aquatic invertebrates.

Major point sources of per- and polyfluoroalkyl substances (PFASs) cause ubiquitous spread of PFASs in the environment. In this study, surface water and aquatic invertebrates at three Swedish sites impacted by PFAS point sources were characterized, using homologue, isomer and extractable organofluorine (EOF) profiling as well as estimation of bioaccumulation factors (BAFs) and mass discharge. Two sites were impacted by fire training (sites A and R) and the third by industrial runoff (site K). Mean Σ25PFASs concentration in water was 1920 ng L-1 at site R (n = 3), which was more than 20- and 10-fold higher than those from sites A and K, respectively. PFOS was the most predominant PFAS in all waters samples, constituting 29-79% of Σ25PFAS concentrations. Several branched isomers were detected and they substantially contributed to concentrations in surface water (e.g. 49-78% of ΣPFOS) and aquatic invertebrates (e.g. 15-28% of ΣPFOS). BAFs in the aquatic invertebrates indicated higher bioaccumulation for long chain PFASs and lower bioaccumulation for branched PFOS isomers compared to linear PFOS. EOF mass balance showed that Σ25target PFASs in water could explain up to 55% of EOF at site R. However, larger proportions of EOF (>92%) remained unknown in water from sites A and K. Mass discharges were for the first time estimated for EOF and revealed that high amounts of EOF (e.g. 8.2 g F day-1 at site A) could be transported by water to recipient water bodies relative to Σ25PFASs (e.g. 0.15 g day-1 at site A). Overall, we showed that composition profiling, BAFs and EOF mass balance can improve the characterization of PFASs around point sources.