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.
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•PFASs were detected in 100% of groundwater samples impacted by recycled water.•∑20PFAS were detected up to 74 ng/L in recycled water impated groundwater.•PFOS, PFBS, PFOA and PFBA were the most frequently detected compounds.•PFOS was detected between <0.03–34 ng/L.
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: <LOQ – 46 ng/L) and PFOA (12 ng/L; range: 1.7–74 ng/L). Positive correlations between ∑14PFAS, PFOA and other perfluoroalkyl carboxylic acids (PFCAs) (e.g. PFHxA) with typical leachate indicators including ammonia-N and bicarbonate were observed. In contrast, no such correlations were found with perfluoroalkyl sulfonic acids (PFSAs) (e.g., PFOS and PFHxS). In addition, a strong positive linear correlation (R2 = 0.69) was found between the proportion of PFOA in the sum of detected perfluorinated alkylated acids (PFOA/∑PFAA) and ammonia-N concentrations in groundwater. This is consistent with previous research showing relatively high PFOA/∑PFAA in municipal landfill leachates, and more conservative behaviour (e.g. less sorption and reactivity) of PFCAs during subsurface transport compared to PFSAs. PFOA/∑PFAA in groundwater may therefore be a useful indicator of municipal landfill-derived PFAA. One site with significantly elevated PFOS and PFHxS concentrations (4,800 and 280 ng/L, respectively) appears to be affected by point-source industrial contamination, as landfill leachate indicators were absent.
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•Groundwater in Australia's largest urban re-development area was analysed for PFAS.•∑14PFAS varied from 26 up to 5,200 ng/L near a potential industrial point-source.•PFOA, PFHxA showed positive correlations with landfill leachate indicators.•Strong positive linear correlation observed between PFOA/∑PFAA and NH3N.•Groundwater PFOA/∑PFAA may be a useful tracer of municipal landfill-derived PFAS.
PFAS have been analysed in groundwater surrounding legacy landfills in a major urban re-development precinct in Australia, to better understand their sources, fate and transport.
An industrial warehouse illegally storing a large quantity of unknown chemical and industrial waste ignited in an urban area in Melbourne, Australia. The multiday fire required firefighters to use ...large amounts of fluorine-free foam that carried contaminated firewater runoff into an adjacent freshwater creek. In this study, the occurrence and fate of 42 per- and polyfluoroalkyl substances (PFASs) was determined from triplicate surface water samples (n = 45) from five locations (upstream, point-source, downstream; 8 km) over three sampling campaigns from 2018 to 2020. Out of the 42 target PFASs, perfluorocarboxylates (PFCAs: C4–C14), perfluoroalkane sulfonates (PFSAs: C4–C10), and perfluoroalkyl acid precursors (e.g. 6:2 fluorotelomer sulfonate (6:2 FTSA)) were ubiquitously detected in surface waters (concentration ranges: <0.7–3000 ng/L). A significant difference in ΣPFAS concentration was observed at the point-source (mean 5500 ng/L; 95% CI: 4800, 6300) relative to upstream sites (mean 100 ng/L; 95% CI: 90, 110; p ≤ 0.001). The point-source ΣPFAS concentration decreased from 5500 ± 1200 ng/L to 960 ± 42 ng/L (−83%) after two months and to 430 ± 15 ng/L (−98%) two years later. 6:2 FTSA and perfluorooctanesulfonate (PFOS) dominated in surface water, representing on average 31% and 20% of the ΣPFAS, respectively. Emerging PFASs including a cyclic perfluoroalkanesulfonate (PFECHS) and a C4 perfluoroalkane sulfonamide (FBSA) were repeatedly present in surface water (concentration ranges <0.3–77 ng/L). According to the updated Australian PFAS guidelines for ecological conservation, the water samples collected at the time of monitoring may have posed a short-term risk to aquatic organisms in regard to PFOS levels. These results illustrate that acute high dose exposure to PFASs can result from industrial fires at sites storing or stockpiling PFAS-based waste products. Continued monitoring will be crucial to evaluate potential long-term risk to wildlife in the region.
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•Up to 42 PFASs were released into an 8 km fresh waterbody from an urban industrial fire.•ΣPFAS levels were up to 70X higher at the point-source than upstream sites.•6:2 FTSA and PFOS were the dominant PFAS released downstream.•ΣPFAS concentrations decreased up to 98% after two years but were still 3–6X higher than upstream sites.•Emerging and novel PFASs were identified for the first time in the Australian environment.
Per- and polyfluoroalkyl substances (PFAS) concentrations were investigated in hepatic tissue of four dolphin species stranded along the south-east coast of Australia between 2006 and 2021; Burrunan ...dolphin (Tursiops australis), common bottlenose dolphin (Tursiops truncatus), Indo-Pacific bottlenose dolphin (Tursiops aduncus), and short-beaked common dolphin (Delphinus delphis). Two Burrunan dolphin populations represented in the dataset have the highest reported global population concentrations of ∑25PFAS (Port Phillip Bay median 9750 ng/g ww, n = 3, and Gippsland Lakes median 3560 ng/g ww, n = 8), which were 50-100 times higher than the other species reported here; common bottlenose dolphin (50 ng/g ww, n = 9), Indo-Pacific bottlenose dolphin (80 ng/g ww, n = 1), and short-beaked common dolphin (61 ng/g ww, n = 12). Also included in the results is the highest reported individual ∑25PFAS (19,500 ng/g ww) and PFOS (18,700 ng/g ww) concentrations, at almost 30 % higher than any other Cetacea reported globally. Perfluorooctane sulfonate (PFOS) was above method reporting limits for all samples (range; 5.3-18,700 ng/g ww), and constituted the highest contribution to overall ∑PFAS burdens with between 47 % and 99 % of the profile across the dataset. The concentrations of PFOS exceed published tentative critical concentrations (677-775 ng/g) in 42 % of all dolphins and 90 % of the critically endangered Burrunan dolphin. This research reports for the first time novel and emerging PFASs such as 6:2 Cl-PFESA, PFMPA, PFEECH and FBSA in marine mammals of the southern hemisphere, with high detection rates across the dataset. It is the first study to show the occurrence of PFAS in the tissues of multiple species of Cetacea from the Australasian region, demonstrating high global concentrations for inshore dolphins. Finally, it provides key baseline knowledge to the potential exposure and bioaccumulation of PFAS compounds within the coastal environment of south-east Australia.
Simultaneous identification and quantification of per- and polyfluoroalkyl substances (PFAS) were evaluated for three quadrupole time-of-flight mass spectrometry (QTOF) acquisition methods. The ...acquisition methods investigated were MS-Only, all ion fragmentation (All-Ions), and automated tandem mass spectrometry (Auto-MS/MS). Target analytes were the 25 PFAS of US EPA Method 533 and the acquisition methods were evaluated by analyte response, limit of quantification (LOQ), accuracy, precision, and target-suspect screening identification limit (IL). PFAS LOQs were consistent across acquisition methods, with individual PFAS LOQs within an order of magnitude. The mean and range for MS-Only, All-Ions, and Auto-MS/MS are 1.3 (0.34–5.1), 2.1 (0.49–5.1), and 1.5 (0.20–5.1) pg on column. For fast data processing and tentative identification with lower confidence, MS-Only is recommended; however, this can lead to false-positives. Where high-confidence identification, structural characterisation, and quantification are desired, Auto-MS/MS is recommended; however, cycle time should be considered where many compounds are anticipated to be present. For comprehensive screening workflows and sample archiving, All-Ions is recommended, facilitating both quantification and retrospective analysis. This study validated HRMS acquisition approaches for quantification (based upon precursor data) and exploration of identification workflows for a range of PFAS compounds.
Graphical Abstract
The field-based distribution and bioaccumulation factor (BAF) for per- and polyfluoroalkyl substances (PFASs) were determined in residential Black Swans (Cygnus atratus) from an urban lake ...(Melbourne, Australia). The concentrations of 46 aliphatic and cyclic PFASs were determined by HPLC-MS/MS in serum and excrement from swans, and water, sediment, aquatic macrophytes, soil, and grass samples in and around the lake. Elevated concentrations of ∑46PFASs were detected in serum (120 ng mL–1) and excrement (110 ng g–1 dw) were strongly related indicating a potential noninvasive sampling methodology. Environmental concentrations of PFASs were consistent with a highly impacted ecosystem and notably high concentrations of perfluoro-4-ethylcyclohexanesulfonate (PFECHS, 67584–42–3; C8HF15SO3) were detected in water (27 ng L–1) and swan serum (16 ng mL–1). In the absence of credible putative alternative sources of PFECHS input to the lake, we propose that the use of high-performance motorsport vehicles is a likely source of contamination to this ecosystem. The BAF of perfluorocarboxylic acids increased with each additional CF2 moiety from PFOA (15.7 L kg–1 ww) to PFDoDA (3615 L kg–1 ww). The BAF of PFECHS was estimated as 593 L kg–1 ww, which is lower compared with that of PFOS (1097 L kg–1 ww).
This study aims to identify sources of per- and polyfluoroalkyl substances (PFAS) to wastewater treatment plants (WWTPs) and reveals previously undescribed variability in daily PFAS concentrations by ...measuring their occurrence in WWTP influent each hour over the course of a week. ∑50PFAS concentrations ranged between 89 ± 38 on Monday and 173 ± 110 ng L-1 on Friday, where perfluoroalkyl carboxylic acids (PFCAs), disubstituted phosphate esters (diPAPs), and perfluoroalkyl sulfonic acids (PFSAs) contributed the largest proportion to overall weekly concentrations 37%, 30%, and 17% respectively. Simultaneous pulse events of perfluorooctanesulfonic acid (PFOS; 400 ng L-1) and perfluoroheptanesulfonic acid (PFHpS; 18 ng L-1) indicate significant industrial or commercial waste discharge that persists for up to 3 h. The minimum number of hourly grab samples required to detect variation of PFOS and PFHpS concentrations are 7 and 9 samples respectively, indicating a high degree of variability in PFAS concentrations between days. Overall, the risk of sampling bias from grab samples is high given the variability in PFAS concentrations and more frequent sampling campaigns must be balanced against the cost of analysis carefully to avoid the mischaracterisation of mass flux to receiving surface waters.
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•Concentrations of 50 PFAS were measured for 168 consecutive hours in WWTP influent.•Daily average ∑50PFAS concentrations differed significantly over 7-days.•A minimum of nine randomly collected grab samples per day is recommended.•Pulse events increase PFAS concentrations up to 10-times compared with daily averages.•Instantaneous grab samples should not be used to estimate annual mass flux.
Microsampling allows the collection of blood samples using a method which is inexpensive, simple and minimally-invasive, without the need for specially-trained medical staff. Analysis of whole blood ...provides a more holistic understanding of per- and polyfluoroalkyl substances (PFAS) body burden. Capillary action microsamplers (Trajan hemaPEN®) allow the controlled collection of whole blood as dried blood spots (DBS) (four 2.74 µL ± 5 %). The quantification of 75 PFAS from DBS was evaluated by comparing five common extraction techniques. Spiked blood (5 ng/mL PFAS) was extracted by protein precipitation (centrifuged; filtered), acid-base liquid-liquid extraction, trypsin protease digestion, and weak anion exchange (WAX) solid-phase extraction with analysis by high-performance liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS). Filtered protein precipitation was the most effective extraction method, recovering 72 of the 75 PFAS within 70 to 130 % with method reporting limit (MRL) for PFOS of 0.17 ng/L and ranging between 0.05 ng/mL and 0.34 ng/mL for all other PFAS. The optimised method was applied to human blood samples to examine Inter- ( n = 7) and intra-day ( n = 5) PFAS blood levels in one individual. Sixteen PFAS were detected with an overall Σ 16 PFAS mean = 6.3 (range = 5.7–7.0) ng/mL and perfluorooctane sulfonate (branched and linear isomers, ΣPFOS) = 3.3 (2.8–3.7) ng/mL being the dominant PFAS present. To the authors knowledge, this minimally invasive self-sampling protocol is the most extensive method for PFAS in blood reported and could be a useful tool for large scale human biomonitoring studies.
Advances in analytical techniques have allowed greater detection of environmental contaminants from small volumes of sample. Four methodologies were evaluated for the extraction of 53 per- and ...polyfluoroalkyl substances (PFASs) from eight classes in 200 µL of avian and mammal serum. Spiked serums at four concentrations (0, 0.5, 5.0 and 25 ng mL
−1
) were prepared by protein precipitation (PPT), enhanced matrix removal (EMR), weak anion exchange (WAX), and hydrophilic-lipophilic balance (HLB) solid-phase extraction cartridges. The extract from each methodology was analysed by high-performance liquid chromatography coupled with tandem mass spectrometry (HPLC–MS/MS), and concentrations were compared with known concentrations in the spiked media. EMR performed the best overall, with 40 of 53 compounds effectively recovered at 5 ng mL
−1
. Furthermore, EMR was effective overall at concentrations ranging from 0.5 to 25 ng mL
−1
for 39 out of 53. Similarly, PPT was effective for 35 of 53 compounds at all spiked serum concentrations. There was a negative correlation between internal standard recovery for compounds with increasing octanol–water coefficients (
K
ow
) for WAX (
R
= − 0.65,
p
= 0.0043) and HLB (
R
= − 0.62,
p
= 0.0077) extractions, indicating methanol may not be a suitable solvent for long-chain PFAS extraction from protein-rich tissues. EMR and PPT represent fast and effective methodologies for the extraction of PFASs from low volumes of serum which allows greater accuracy and precision that can be applied to future human and wildlife biomonitoring programmes.
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