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Trifluoroacetic Acid (TFA) as a Planetary Boundary Threat

Arp, Hans Peter H.; Gredelj, Andrea; Glüge, Juliane; Scheringer, Martin; Cousins, Ian

Abstract

Trifluoroacetic acid (TFA) belongs to the subclass of per- and polyfluoroalkyl substances (PFAS) known as ultra-short chain perfluoroalkyl acids (PFAAs). The initial wave of scientific interest surrounding TFA started in the mid-1990s and was related to the introduction of F-gases as novel refrigerants, as TFA is their common degradation product. F-gases were introduced after chlorofluorocarbons (CFC) were phased out under the 1987 Montreal Protocol on Substances that Deplete the Ozone Layer. In recent years, TFA has been commonly measured and reported alongside other PFAS, with alarmingly high concentrations detected across various environmental matrices, making TFA the most abundant PFAS in the environment.[1] Although early studies suggested that TFA and other short-chain PFAAs are less hazardous than long-chain PFAAs - due to their lower bioaccumulation in lipids and lower direct toxicity - more recent evidence highlights concerns about TFA's environmental persistence and very high accumulation in water matrices and especially plants. Although there are fewer toxicological data compared to long-chain PFAAs, we maintain that there are more than sufficient data to conclude that TFA poses a risk to humans and the environment and meets the criteria of a planetary boundary threat for novel entities.[1] We performed an analysis of the scientific literature on TFA to assess if there is sufficient evidence of its exceedance of a planetary boundary. According to Persson et al.[3], chemical poses a planetary boundary threat if three conditions are met: “Condition 1 (C1) – the pollution has a disruptive effect on a vital earth system process of which we are ignorant; Condition 2 (C2) – the disruptive effect is not discovered until the associated impacts are, or inevitably will be, manifested at a global scale; and Condition 3 (C3) the impacts are poorly reversible because the level of pollution in the global environment cannot be readily reduce”. To assess whether TFA meets these conditions, a review and analysis of the existing body of scientific literature on TFA’s environmental effects and exposure were conducted. In addition, current health advisory and regulatory values were assessed in this context. A review of the scientific literature was conducted to obtain an overview of average and maximum concentrations in diverse environmental media, with 43 studies spanning from the late 1990s to the 2020s selected and monitoring data reporting on TFA concentrations were analyzed. These were compared with potential disruptive effects on human health and the environment. We conclude from this that Condition 1 (C1) is fulfilled based on the many known and unknown thresholds that could be exceeded of which we are ignorant. Condition 2 (C2) is fulfilled as TFA is already present globally in all environmental media and Condition 3 (C3) is satisfied because the effects of TFA, once realized, will be irreversible for the foreseeable future, owing to its high persistence, mobility, and emissions from multiple sources. Acknowledgments. European Union’s Horizon 2020 research and innovation program project ZeroPM, under grant agreement No 101036756, and the Horizon Europe project ARAGORN under grant agreement 101112723.

Full text

This project has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 101036756. Trifluoroacetic Acid (TFA) as a Planetary Boundary Threat Hans Peter H. Arp1,2, Andrea Gredelj1, Juliane Glüge3, Martin Scheringer3,4 and Ian Cousins5 1Norwegian Geotechnical Institute, Oslo, Norway; 2Norwegian University of Science and Technology, Trondheim, Norway; 3 Institute of Biogeochemistry and Pollutant Dynamics, ETH Zürich, Zürich Switzerland, 4RECETOX, Masaryk University, Brno, Czech Republic, 5Department of Environmental Science, Stockholm University, Stockholm, Sweden Contents •Increasing Sources Irreversible Effects Solutions to a Global Threat TFA is accumulating everywhere, largely coinciding with F-gas use following the Montreal Protocol and TFA use in many pesticides and other products TFA accumulating in arctic ice cores Pickard et al. Geophysical Research Letters (2020),47, e2020GL087535 Freeling and Björnsdotter, Current Opinion in Green and Sustainable Chemistry 2023, 41:100807 and in tree leaves and in groundwater Albers and Sültenfuss, Environmental Science & Technology Letters 2024 11 (10), 1090-1095 Drinking water (median)1,2 •Germany: 1.5 µg/L •19 Countries: 0.23 µg/L Tee (median): 2.4 µg/L2 Beer (median) 6.1 µg/L2 Orange juice (mean 34 µg/L)3 Apple juice (mean 6.2 µg/L)3 1. Neuwald et al. Environmental Science & Technology 2022 56 (10), 6380-6390 2. Scheurer & Nödler. Food Chemistry,351, 129304. 3. Van Hees et al. https://cdnmedia.eurofins.com/europeaneast/media/uxcnaa2c/eurofins_tfa_tfms_juice_24_final.pdf TFA is increasing in all that we drink Wine image: Sai Balaji Varma Gadhiraju Unpublished data: Michael Müller. Uni. Freiburg [email protected] (used with permission) …Wine PAN Europe: Message from the Bottle –The Rapid Rise of TFA Contamination Across the EU Up to 300 µg/L TFA is p Scheurer und Nödler Food Chemistry 351 (2021) 129304 µg/kg dw TFA is accummulating everywhere it can be measured Chinese blood 97% detection Median 8.5 µg/L Similar to levels of the sum of all long-chain, bioaccumulative PFAS Duan et al. (2020) Environ Int 134:105295. Zheng et al. (2023) ES&T 2023, 57, 15782-15793 Arp et al. ES&T 2024, 58, 45, 19925-19935 USA blood serum 74% detection Median 6.0 µg/L Twice the levels of the sum of all long-chain, bioaccumulative PFAS What levels of TFA will be in the blood of future generations? What will the impact of this be No evidence that TFA is of natural origin Hypothesis (2001-2005) of a natural origin of TFA in the deep oceans1,2 Hypothesis no longer supported3 •No TFA gradients by deep sea vents •TFA, PFAS and other synthetic substances in deep sea via oceanic currents sinking of dense water formed on continental shelfs Marine snow deposition •Inconsistent with time trends in rain/ice cores 1) Frank et al. Environmental Science & Technology 2002 36 (1), 12-15 2) Scott et al. Environmental Science & Technology 2005 39 (17), 6555-6560 3) Joudan et al. Environ. Sci.: Processes Impacts, 2021,23, 1641-1649 No natural sources Pesticide/Herbicide precursors lead to TFA hotspots in agricultural areas Joerss et al. (2024) Environment International,193, 109061. Major precursors trifluralin fluometuron Major precursors: flufenacet oxyfluorfen Pharmaceuticals Bicalutamide – since 1995 (prostate cancer treatment) Celecoxib –since 1999 (Non-steroidal antiinflammatory) Efavirenz – since 1998 (HIV/AIDS treatment) Flecainide –since 1985 (fast heart-rate treatment) Fluoxetine (Prozac) - since1986 (Anti-depressant) Sitagliptin –since 2006 (Anti-diabetic) Sludge/biosolid Agricultural chemicals Planetary Boundary Threat of TFA TFA emissions Disturbances to the «homeostasis» or of earth processes. Exceed this, Earth would leave the Holocene where humans evolved. Conditions for novel entities:1,2 Condition 1: pollution disrupts a vital earth system process of which we are ignorant. TRUE: impacts at hotspots occur now, ignorant of impacts from life-long intergeneration exposure (ignorant) Condition 2: disruptive effect is not discovered until …manifested at a global scale TRUE: TFA increases globally Condition 3: impacts are poorly reversible because level of global pollution cannot be readly reduced TRUE: TFA is already diluted, stock piles of sources exist. Most TFA we emit will exist in water for the future of earth 1. Persson et al. Environ. Sci. Technol.2013,47 (22), 12619–12622 2. MacLeod et al. Science 373,61-65(2021) Impacts persiste even after phaseout. What will the severity be? Pesticides and Pharmaceuticals •TFA precursor Flufanecet to be non-renewed in Europe (draft decision) •more of this! https://efsa.onlinelibrary.wiley.com/doi/epdf/10.2903/j.efsa.2024.8997 Barbu (2024). https://pubs.acs.org/doi/pdf/10.1021/cen-10226-feature1 •Biodegradable, non-fluorinated drugs an active area of «green pharmacy» innovation •Evaluate switching to PFAS free alternatives when recommending medications Solution to F-gases used as refrigerants Refrigerants and blowing agents Fifth generation of F-gases in the Montreal Protocol can be free of TFA precursors Effective Communication and Labelling Ellise Suffill, ZeroPM pieces #17 -Expert & non-expert perceptions on PFAS & essentiality in everyday products. https://zenodo.org/records/10628255 Solutions to a global threat: Transition to alternative technologies that do not involve precursors to TFA Better understand the exposure irreversible impacts of TFA on soil, plants, microbes and humans Safely dispose existing stockpiles and hotspots of TFA-precursors Acknowledgements Thanks to funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 101036756 2021-2026 https://zeropm.eu/ https://zeropm.eu/removal-workshop/ Submission Deadline: September 30, 2025