Per- and polyfluoroalkyl substances (PFAS) in little penguins and associations with urbanisation and health parameters.

Per- and Polyfluoroalkyl substances (PFAS) are increasingly detected in wildlife and present concerning and unknown health risks. While there is a growing body of literature describing PFAS in seabird species, knowledge from temperate Southern Hemisphere regions is lacking. Little penguins (Eudyptula minor) can nest and forage within heavily urbanised coastal environments and hence may be at risk of exposure to pollutants. We analysed scat contaminated nesting soils (n = 50) from 17 colonies in lutruwita/Tasmania for 16 PFAS, plasma samples (n = 45) from nine colonies, and three eggs for 49 PFAS. We detected 14 PFAS across the sample types, with perfluorooctanesulfonic acid (PFOS) and perfluorohexanesulfonic acid (PFHxS) most commonly detected. Mean concentration of PFOS in plasma was 2.56 ± 4.3 ng/mL (

Exposure to Environmentally Relevant Levels of PFAS Causes Metabolic Changes in the Freshwater Amphipod Austrochiltonia subtenuis.

Per and polyfluoroalkyl substances (PFAS) are of concern to environmental regulators due to their widespread occurrence, persistence and reported toxicity. However, little data exist on the effects of PFAS at environmentally relevant concentrations. The development of molecular markers for PFAS exposure would therefore be useful to better understand the environmental risks of these compounds. In this study, we assessed if such markers could be developed using Gas Chromatography-Mass Spectrometry-based metabolomics. We exposed the freshwater amphipod Austrochiltonia subtenuis to a range of environmentally relevant concentrations of perfluoro-octane sulfonic acid (PFOS), hexafluoropropylene oxide dimer acid (GenX) and perfluorohexanesulphonic acid (PFHxS) for 7 days at five concentrations. A metabolic response was detected in all concentrations and treatments even though the survival rates only differed significantly at the highest exposure levels. The metabolic response differed between compounds but all three PFAS induced changes in the levels of amino acids, fatty acids, and cholesterol, in line with the literature. PFOS was found to bioaccumulate. Both GenX and PFHxS were eliminated from the amphipods, but PFHxS was eliminated at a slower rate than GenX. This information improves our understanding of the sublethal effects of PFAS as well as their environmental fate and behaviour.

Dietary Uptake and Depuration Kinetics of Perfluorooctane Sulfonate, Perfluorooctanoic Acid, and Hexafluoropropylene Oxide Dimer Acid (GenX) in a Benthic Fish.

Per- and poly-fluoroalkyl substances (PFAS) are ubiquitously distributed throughout aquatic environments and can bioaccumulate in organisms. We examined dietary uptake and depuration of a mixture of 3 PFAS: perfluorooctanoic acid (PFOA; C8 HF15 O2 ), perfluorooctane sulfonate (PFOS; C8 HF17 SO3 ), and hexafluoropropylene oxide dimer acid (HPFO-DA; C6 HF11 O3 ; trade name GenX). Benthic fish (blue spot gobies, Pseudogobius sp.) were fed contaminated food (nominal dose 500 ng g-1 ) daily for a 21-d uptake period, followed by a 42-d depuration period. The compounds PFOA, linear-PFOS (linear PFOS), and total PFOS (sum of linear and branched PFOS) were detected in freeze-dried fish, whereas GenX was not, indicating either a lack of uptake or rapid elimination (<24 h). Depuration rates (d-1 ) were 0.150 (PFOA), 0.045 (linear-PFOS), and 0.042 (linear+branched-PFOS) with corresponding biological half-lives of 5.9, 15, and 16 d, respectively. The PFOS isomers were eliminated differently, resulting in enrichment of linear-PFOS (70-90%) throughout the depuration period. The present study is the first reported study of GenX dietary bioaccumulation potential in fish, and the first dietary study to investigate uptake and depuration of multiple PFASs simultaneously, allowing us to determine that whereas PFOA and PFOS accumulated as expected, GenX, administered in the same way, did not appear to bioaccumulate. Environ Toxicol Chem 2020;39:595-603. © 2019 SETAC.

An investigation into per- and polyfluoroalkyl substances (PFAS) in nineteen Australian wastewater treatment plants (WWTPs).

Quantifying the emissions of per- and polyfluoroalkyl substances (PFAS) from Australian wastewater treatment plants (WWTP) is of high importance due to potential impacts on receiving aquatic ecosystems. The new Australian PFAS National Environmental Management Plan recommends 0.23 ng L-1 of PFOS as the guideline value for 99% species protection for aquatic systems. In this study, 21 PFAS from four classes were measured in WWTP solid and aqueous samples from 19 Australian WWTPs. The mean ∑21PFAS was 110 ng L-1 (median: 80 ng L-1; range: 9.3-520 ng L-1) in aqueous samples and 34 ng g-1 dw (median: 12 ng g-1 dw; range: 2.0-130 ng g-1 dw) in WWTP solids. Similar to WWTPs worldwide, perfluorocarboxylic acids were generally higher in effluent, compared to influent. Partitioning to solids within WWTPs increased with increasing fluoroalkyl chain length from 0.05 to 1.22 log units. Many PFAS were highly correlated, and PCA analysis showed strong associations between two groups: odd chained PFCAs, PFHxA and PFSAs; and 6:2 FTS with daily inflow volume and the proportion of trade waste accepted by WWTPs (as % of typical dry inflow). The compounds PFPeA, PFHxA, PFHpA, PFOA, PFNA, and PFDA increased significantly between influent and final effluent. The compounds 6:2 FTS and 8:2 FTS were quantified and F-53B detected and reported in Australian WWTP matrices. The compound 6:2 FTS was an important contributor to PFAS emissions in the studied Australian WWTPs, supporting the need for future research on its sources (including precursor degradation), environmental fate and impact in Australian aquatic environments receiving WWTP effluent.

A single analytical method for the determination of 53 legacy and emerging per- and polyfluoroalkyl substances (PFAS) in aqueous matrices.

A quantitative method for the determination of per- and polyfluoroalkyl substances (PFAS) using liquid chromatography (LC) tandem mass spectrometry (MS/MS) was developed and applied to aqueous wastewater, surface water, and drinking water samples. Fifty-three PFAS from 14 compound classes (including many contaminants of emerging concern) were measured using a single analytical method. After solid-phase extraction using weak anion exchange cartridges, method detection limits in water ranged from 0.28 to 18 ng/L and method quantitation limits ranged from 0.35 to 26 ng/L. Method accuracy ranged from 70 to 127% for 49 of the 53 extracted PFAS, with the remaining four between 66 and 138%. Method precision ranged from 2 to 28% RSD, with 49 out of the 53 PFAS being below < 20%. In addition to quantifying > 50 PFAS, many of which are currently unregulated in the environment and not included in typical analytical lists, this method has efficiency advantages over other similar methods as it utilizes a single chromatographic separation with a shorter runtime (14 min), while maintaining method accuracy and stability and the separation of branched and linear PFAS isomers. The method was applied to wastewater influent and effluent; surface water from a river, wetland, and lake; and drinking water samples to survey PFAS contamination in Australian aqueous matrices. The compound classes FTCAs, FOSAAs, PFPAs, and diPAPs were detected for the first time in Australian WWTPs and the method was used to quantify PFAS concentrations from 0.60 to 193 ng/L. The range of compound classes detected and different PFAS signatures between sample locations demonstrate the need for expanded quantitation lists when investigating PFAS, especially newer classes in aqueous environmental samples. Graphical abstract.

Contamination of groundwater with per- and polyfluoroalkyl substances (PFAS) from legacy landfills in an urban re-development precinct.

The extent of per- and polyfluoroalkyl substances (PFAS) in groundwater surrounding legacy landfills is currently poorly constrained. Seventeen PFAS were analysed in groundwater surrounding legacy landfills in a major Australian urban re-development precinct. Sampling locations (n = 13) included sites installed directly in waste material and down-gradient from landfills, some of which exhibited evidence of leachate contamination including elevated concentrations of ammonia-N (≤106 mg/L), bicarbonate (≤1,740 mg/L) and dissolved methane (≤10.4 mg/L). Between one and fourteen PFAS were detected at all sites and PFOS, PFHxS, PFOA and PFBS were detected in all samples. The sum of detected PFAS (∑14PFAS) varied from 26 ng/L at an ambient background site to 5,200 ng/L near a potential industrial point-source. PFHxS had the highest median concentration (34 ng/L; range: 2.6-280 ng/L) followed by PFOS (26 ng/L; range: 1.3-4,800 ng/L), PFHxA (19 ng/L; range:

Investigating recycled water use as a diffuse source of per- and polyfluoroalkyl substances (PFASs) to groundwater in Melbourne, Australia.

The purpose of this study was to investigate the contribution of per- and polyfluoroalkyl substances (PFASs) to groundwater at a location where recycled water from a wastewater treatment plant (WWTP) is used to irrigate crops. Groundwater from Werribee South, located west of Melbourne, Australia, was sampled over two campaigns in 2017 and 2018, extracted using solid phase extraction (SPE) and analysed with liquid chromatography-tandem mass spectrometry (LC-MS/MS-QQQ). PFASs were detected in 100% of the groundwater samples. The sum total of twenty PFAS compounds (∑20PFASs) for all sites in the study ranged from <0.03 to 74 ng/L (n = 28) and the highest levels of which were observed in the centre of the irrigation district. Perfluorooctanesulfonic acid (PFOS) was the most detected compound overall (96%) with a mean concentration of 11 ng/L (<0.03-34 ng/L), followed by perfluorobutanesulfonic acid (PFBS; 86%, 4.4 ng/L), perfluorooctanoic acid (PFOA; 82%, 2.2 ng/L) and perfluorobutanoic acid (PFBA; 77%, 6.1 ng/L). Concentrations of PFASs found in this study are greater than background levels of PFASs detected in groundwater and are in the range of concentrations typically detected in wastewater effluent. This study presents evidence that the use of recycled water can be a source of PFAS contamination to groundwater.

Impacts on the seagrass, Zostera nigricaulis, from the herbicide Fusilade Forte® used in the management of Spartina anglica infestations.

The herbicide Fusilade Forte® (FF) is widely applied in agricultural weed management and in the management of the invasive saltmarsh grass, Spartina anglica (ricegrass or cordgrass). FF (active ingredient fluazifop-P acid, FPA) is selective for poaceous grasses. Its primary mode of action is inhibition of the acetyl coenzyme-A carboxylase (ACCase) specific to this taxonomic group, and its secondary mode is by promotion of oxidative stress. FF is applied to S. anglica infestations in the intertidal zone, in proximity to seagrass meadows. Despite the potential for vital seagrass ecosystems to be exposed to FF, there is limited knowledge of any potential impacts. We investigated impacts of FPA on the endemic Australian seagrass, Zostera nigricaulis, measuring ACCase activity and parameters that reflect oxidative stress: photosynthetic performance, lipid peroxidation and photosynthetic pigment content. Seagrass was exposed to FF (0.01-10mgL-1 FPA and a control) for 7d, followed by a 7-d recovery in uncontaminated seawater. An enzyme assay demonstrated that FPA ≤10mgL-1 did not inhibit the activity of ACCase isolated from Z. nigricaulis, demonstrating that this seagrass is resistant to FF's primary mode of action. However, physiological impacts occurred following 7 days exposure to ≥0.1mgL-1 FPA, including up to a 72% reduction in photosynthetic pigment concentration. After 7-d recovery, photosynthetic pigment content improved in treatment plants; however, treated plants exhibited higher levels of lipid peroxidation. This study demonstrates that while Z. nigricaulis is resistant to FF's primary mode of action, significant physiological impacts occur following 7 days exposure to ≥0.1mgL-1 FPA. This study provides valuable information on the effects of FF on a non-target species that can better inform approaches to Spartina management in coastal seagrass ecosystems.

The psychoactive pollutant fluoxetine compromises antipredator behaviour in fish.

Pharmaceuticals are increasingly being detected in aquatic ecosystems worldwide. Particularly concerning are pharmaceutical pollutants that can adversely impact exposed wildlife, even at extremely low concentrations. One such contaminant is the widely prescribed antidepressant fluoxetine, which can disrupt neurotransmission and behavioural pathways in wildlife. Despite this, relatively limited research has addressed the behavioural impacts of fluoxetine at ecologically realistic exposure concentrations. Here, we show that 28-day fluoxetine exposure at two ecologically relevant dosages-one representing low surface water concentrations and another representing high effluent flow concentrations-alters antipredator behaviour in Eastern mosquitofish (Gambusia holbrooki). We found that fluoxetine exposure at the lower dosage resulted in increased activity levels irrespective of the presence or absence of a predatory dragonfly nymph (Hemianax papuensis). Additionally, irrespective of exposure concentration, fluoxetine-exposed fish entered the predator 'strike zone' more rapidly. In a separate experiment, fluoxetine exposure reduced mosquitofish freezing behaviour-a common antipredator strategy-following a simulated predator strike, although, in females, this reduction in behaviour was seen only at the lower dosage. Together, our findings suggest that fluoxetine can cause both non-monotonic and sex-dependent shifts in behaviour. Further, they demonstrate that exposure to fluoxetine at environmentally realistic concentrations can alter antipredator behaviour, with important repercussions for organismal fitness.