Elevated Levels of Ultrashort- and Short-Chain Perfluoroalkyl Acids in US Homes and People.

Per- and polyfluoroalkyl substances (PFAS) make up a large group of fluorinated organic compounds extensively used in consumer products and industrial applications. Perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA), the two perfluoroalkyl acids (PFAAs) with 8 carbons in their structure, have been phased out on a global scale because of their high environmental persistence and toxicity. As a result, shorter-chain PFAAs with less than 8 carbons in their structure are being used as their replacements and are now widely detected in the environment, raising concerns about their effects on human health. In this study, 47 PFAAs and their precursors were measured in paired samples of dust and drinking water collected from residential homes in Indiana, United States, and in blood and urine samples collected from the residents of these homes. Ultrashort- (with 2 or 3 carbons [C2-C3]) and short-chain (with 4-7 carbons [C4-C7]) PFAAs were the most abundant in all four matrices and constituted on average 69-100% of the total PFAA concentrations. Specifically, trifluoroacetic acid (TFA, C2) and perfluoropropanoic acid (PFPrA, C3) were the predominant PFAAs in most of the samples. Significant positive correlations (n = 81; r = 0.23-0.42; p < 0.05) were found between TFA, perfluorobutanoic acid (PFBA, C4), and perfluoroheptanoic acid (PFHpA, C7) concentrations in dust or water and those in serum, suggesting dust ingestion and/or drinking water consumption as important exposure pathways for these compounds. This study demonstrates that ultrashort- and short-chain PFAAs are now abundant in the indoor environment and in humans and warrants further research on potential adverse health effects of these exposures.

Increases in Trifluoroacetate Concentrations in Surface Waters over Two Decades.

Trifluoroacetate (TFA) is a persistent perfluorinated alkanoic acid anion that has many anthropogenic sources, with fluorocarbon refrigerants being a major one. After an initial burst of research in the late 1990s and early 2000s, research on this ubiquitous pollutant declined as atmospheric emissions of the precursor compounds grew rapidly. Thus, there is little contemporaneous information about the concentrations of TFA in the environment and how they have changed over time. This research determined the change in TFA concentrations in streams by resampling a transect that was originally sampled in 1998. The transect was designed to determine the regional distribution of TFA both upwind and downwind of major metropolitan areas in Northern California as well as a set of globally remote sites in Alaska. The results showed that TFA concentrations increased by an average of 6-fold over the intervening 23 years, which resulted in a median concentration of 180 ng/L (range 21.3-2790). The highest concentrations were found in streams immediately downwind of the San Francisco Bay Area, while substantially lower concentrations were found in the upwind, regionally remote, and globally remote sites. The C3 to C5 perfluorinated alkanoic acids were also investigated, but they were rarely detected with this methodology.

Ultra-Short-Chain PFASs in the Sources of German Drinking Water: Prevalent, Overlooked, Difficult to Remove, and Unregulated.

Per- and polyfluoroalkyl substances (PFASs) have been a focal point of environmental chemistry and chemical regulation in recent years, culminating in a shift from individual PFAS regulation toward a PFAS group regulatory approach in Europe. PFASs are a highly diverse group of substances, and knowledge about this group is still scarce beyond the well-studied, legacy long-chain, and short-chain perfluorocarboxylates (PFCAs) and perfluorosulfonates (PFSAs). Herein, quantitative and semiquantitative data for 43 legacy short-chain and ultra-short-chain PFASs (≤2 perfluorocarbon atoms for PFCAs, ≤3 for PFSAs and other PFASs) in 46 water samples collected from 13 different sources of German drinking water are presented. The PFASs considered include novel compounds like hexafluoroisopropanol, bis(trifluoromethylsulfonyl)imide, and tris(pentafluoroethyl)trifluorophosphate. The ultra-short-chain PFASs trifluoroacetate, perfluoropropanoate, and trifluoromethanesulfonate were ubiquitous and present at the highest concentrations (98% of sum target PFAS concentrations). "PFAS total" parameters like the adsorbable organic fluorine (AOF) and total oxidizable precursor (TOP) assay were found to provide only an incomplete picture of PFAS contamination in these water samples by not capturing these highly prevalent ultra-short-chain PFASs. These ultra-short-chain PFASs represent a major challenge for drinking water production and show that regulation in the form of preventive measures is required to manage them.

70 analyte PFAS test method highlights need for expanded testing of PFAS in drinking water.

In this community-led pilot study we sought to investigate the utility of expanded per- and polyfluoroalkyl substances (PFAS) testing for drinking water, using a targeted analysis for 70 PFAS and the Total Oxidizable Precursor (TOP) Assay which can indicate the presence of precursor PFAS. PFAS were detected in 30 out of 44 drinking water samples across 16 states; 15 samples would exceed US EPA's proposed maximum contaminant levels for six PFAS. Twenty-six unique PFAS were identified, including 12 not covered by either US EPA Methods 537.1 or 533. An ultrashort chain PFAS, PFPrA, had the highest frequency of detection, occurring in 24 of 30 samples. It was also the PFAS reported at the highest concentration in 15 of these samples. We created a data filter to model how these samples would be reported under the upcoming fifth Unregulated Contaminant Monitoring Rule (UCMR5) requirements. All of the 30 samples with PFAS quantified by the 70 PFAS test had one or more PFAS present that would not be captured if the UCMR5 reporting requirements were followed. Our analysis suggests the upcoming UCMR5 will likely underreport PFAS in drinking water, due to limited coverage and higher minimum reporting limits. Results were inconclusive on the utility of the TOP Assay for monitoring drinking water. The results from this study provide important information to community participants regarding their current PFAS drinking water exposure. In addition, these results suggest gaps that need to be addressed by regulatory and scientific communities, in particular, the need for expanded targeted analysis of PFAS, the development of a sensitive, broad spectrum PFAS test, and further investigation into ultrashort chain PFAS.

Occurrence and fate of poly- and perfluoroalkyl substances (PFAS) in urban waters of New Zealand.

Information on the occurrence of PFAS in aquatic matrices of countries with no PFAS manufacturing, e.g., New Zealand, is limited. Also, the fingerprint of PFAS along an urban water cycle, following water path from wastewater treatment plant (WWTP) effluent to treated drinking water has not been widely assessed. Hence, 38 long-, short-, ultrashort-chain PFAS and fluorinated alternatives (including precursors) were monitored in this study by collecting composite samples from two urban WWTPs of New Zealand and grab samples from the water bodies receiving the WWTPs' effluents and a drinking water treatment plant, whose source water received the effluent of one of the studied WWTPs. ∑PFAS at concentrations 0.1 - 13 ng/L were detected in all wastewater samples, including influents and different treatment stages of the two WWTPs (WW1 and WW2). The fate of most PFAS was similar in the two WWTPs, despite large differences in WWTPs' PFAS loads in the influents, serving populations (1.6 vs 0.16 million), total capacities (300 vs 54 million liters per day), and designs (aerobic and anoxic secondary treatment vs aerobic only). The fate of PFAS in WWTPs appeared to be driven by a range of processes. For instance, a simultaneous increase (41.6%) in short-chain perfluorohexanoic acid (PFHxA) concentrations and decrease (49.7%) in precursor 6:2 fluorotelomer sulfonate (6:2 FTS) concentrations after secondary biological treatment suggested possible transformation of 6:2 FTS into PFHxA during the treatment. In contrast, the reason behind an average decrease of 35% in ultrashort-chain perfluoropropionic acid (PFPrA) concentrations after treatment was unclear, and further studies are recommended. The concentrations of a linear isomer of long-chain perfluorosulfonic acid (PFOS-L) decreased (48%) in the effluent, possibly due to its partitioning to sludge. Although the concentrations of PFAS in coastal waters suggested that the WW1 effluent is a potential source of PFAS, earlier dispersion model and no detection of PFAS in the receiving waters of WW2 implied that other sources, such as septic systems, peripheral industries, and the airport, could also be contributing to PFAS in coastal waters. The source of ultrashort-chain PFPrA (5.5 ng/L) detected in the treated drinking water produced from that river was unclear. The monitoring results confirm incomplete removal of PFAS in WWTPs, indicate a possible transformation of unknown precursors present in wastewater into short-chain perfluoroalkylcarboxylic acids (PFCAs) during biological treatment, and reveal a possible accumulation of perfluoroalkylsulfonic acids (PFSAs) in the sludge, overall suggesting the circulation of PFAS in urban water systems.

Prevalence of per- and polyfluoroalkyl substances (PFASs) in drinking and source water from two Asian countries.

The present study focuses on the determination of the occurrence and levels of per- and polyfluoroalkyl substances (PFASs) in the drinking and source water from the Philippines and Thailand. A total of 46 samples (18 commercial bottled waters, 5 drinking water from vending machine (re-fill stations) and 23 source water) were analyzed using liquid chromatography with tandem high-resolution mass spectrometry. Using the targeted method, 12 different PFASs were detected in the drinking water samples with total quantifiable PFASs (∑PFASs) levels ranging from 7.16 to 59.49 ng/L; 15 PFASs were detected in source water with ∑PFASs ranging from 15.55 to 65.65 ng/L. A 100% detection frequency was observed for perfluoroheptanoic acid (PFHpA), perfluorooctanoic acid (PFOA), perfluorononanoic acid (PFNA), and perfluorosulfonic acid (PFOS) in all water samples. Six other PFASs, not included in the targeted analysis, were detected using the suspect screening approach. For the first time, the presence of 2-(N-methylperfluorooctanesulfonamido) acetic acid (N-MeFOSAA) in drinking water is reported, and 3 novel PFASs (C5H5OF8, C6H4O2F6, and C9H2O2F16) were detected using suspect screening in source water. Combined results from target and suspect screening analysis showed that PFASs detected were predominantly (52%) short-chain (with fluorinated alkyl chain of ≤6) which could be explained by their high mobility in the environment. The detected PFASs levels in drinking water will not likely pose immediate health risk to consumers according to US EPA health advisory for PFOS and PFOA of 70 ng/L, but inclusion of bottled and drinking water from re-fill stations in monitoring programs is warranted.