Trifluoroacetic Acid: a planetary boundary threat - a Webinar for the Tribal PFAS Working Group

Studyon Trifluoroaceticacid (TFA) Join via Zoom by clicking HERE Meeting ID: 860 9712 2226 Password: 368789 Hans Peter H. Arp, PhD Professor at the Norwegian University of Science and Technology and Norwegian Geotechnical Institute Our featured presenter Hans Peter H. Arp discusses the study on trifluoroacetic acid (TFA) and its persistence in the environment. Trifluoroacetic acid is one of the ultrashort chain perfluoroalkyl acids and is a transformation product of PFAS. Join us on Thursday, December 11th 11 AM (PST)/12 PM (MST)/1 PM (CST) This project has received funding from the European Union’s Horizon 2020 research and innovation programme under grant agreement No 101036756. Trifluoroacetic Acid: a planetary boundary threat Hans Peter H. Arp Norwegian Geotechnical Institute (NGI) & Norwegian University of Science and Technology (NTNU) Contact: [email protected] Webinar James Lovelock (1919 – 2022) https://en.wikipedia.org/wiki/James_Lovelock •Invented the Electron Capture Detector (ECD) •First to detect chlorofluorocarbons (CFCs) in the atmosphere •CFCs pose “no conceivable hazard” Lovelock J (1988). The Ages of Gaia: A Biography of Our Living Earth •CFCs pose “no conceivable toxic hazard” Lovelock J (2000). Homage to Gaia: The Life of an Independent Scientist http://www.nasa.gov/vision/earth/environment/ozone_resource_page.html A precautionary tale…. The Montreal Protocol saved the planet. without it there would be no photosynthesis EU and global relative consumption of ozone depleting substances (ODS, like chlorofluorocarbons) since 1986, showing the reduction the consumption of ODS due to the Montreal Protocol. EEA (2023) EU and global consumption of controlled ozone-depleting substances —European Environment Agency. In: European Environmental Agency. 826 https://svs.gsfc.nasa.gov/cgi-bin/details.cgi?aid=10824 Chirsir, Palm et al. (2024 in press), ESEU, DOI: 10.26434/chemrxiv-2024-tn5t5 The history of the Montreal Protocol is a history of burden shifting via «drop in substitution» •1st Gen: Chlorofluorocarbons (CFCs) –Ozone depletion •2nd Gen: Hydrochlorofluorocarbons (HCFCs)– less ozone depleting, but green house gases •3rd Gen: Saturated hydrofluorocarbons (HFCs) -> green house gases, mild formation of TFA •4th Gen: F-gases after Kigali amendment (2019): Unsaturated hydrofluoroolefins (HFOs), less global warming potential, increased formation of TFA 1,1,1,2-Tetrafluoroethane (HFC-134a, Norflurane) Triflouroacetic acid (TFA) Yield between 723% Extremely persistent and mobile Accumulates in the environment ℎ � υ high global warming potential 2,3,3,3Tetrafluoropropene (µHFC-1234yf ) ℎ � υ low global warming potential TFA Yield = 100% ! TFA is accumulating everywhere, largely coinciding with F-gas use following the Montreal Protocol 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 leafs 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 Release from PFAS production and products Joudan et al. Environ. Sci. Technol. Lett.2024, 11, 3, 237-242 Richard Hurd •EU production of TFA 100 –1000 tonnes/year •TFA releases during F-gas, Fluoropolymer and PFAS production (e.g. 7500 µg/L in river Arias near a PFAS production facility)1 1https://www.generations-futures.fr/wp-content/uploads/2024/02/rapport-salindres-pfas.pdf •Fluoropolymers and plastics leach TFA •126 +/-96 µg/kg TFA leach from FEP tubing •1 to 7 µg/kg TFA leach from PVC tubing PFAS production and products Water treatment ineffective at removing TFA, ….or can form TFA Scheurer et al. (2017). Water research,126, 460-471. PFAS remediation •Enhanced degradation techniques (ozonation, chlorination, photolysis, electrolysis, incineration, pyrolysos etc.) can lead to TFA formation from precursors (along with other PFAS, F-gases) •Sorption techniques (activated carbon, ion exchange resins) -> do not filter TFA •Reverse osmosis only technique that works for TFA, but requires an expensive destruction step for brines Water treatment ineffective at removing TFA, ….or can form TFA Scheurer et al. (2017). Water research,126, 460-471. PFAS remediation •Sorption techniques (activated carbon, ion exchange resins) -> do not filter TFA •Enhanced degradation techniques (ozonation, chlorination, photolysis, electrolysis, incineration, pyrolysos etc.) can lead to TFA formation from precursors (along with other PFAS, Fgases) •Reverse osmosis only technique that works for TFA, but requires an expensive destruction step for brines The absurd costs of TFA remediation… •Recent collaboration with Forever Pollution Project and Prof. Ali Ling •Cost to remediate emerging ultra-short chain PFAS like TFA in Europe 100 billion EUR/y (ca 100 billion USD/y) for water and soil •Combination of reverse osmosis and super critical water oxidation for brines •Would make drinking water more expensive and no longer mineral…. •Still be exposed to TFA…the wine will still be contaminated.. https://foreverpollution.eu/lobbying/ Irreversible effects mammals Aquatic algae / microbes Soils / terrestrial ecosystems Planetary boundaries RIVM (2022) Chronic rat toxicity (feeding) Dose response: Male liver weight vs dose Relevant potency factor: TFA is 0.002 x toxic as PFOA Corresponds to a water threshold value of 2.2 µg/L Exceeded in an increasing number of areas Toxicity to Mammals https://www.rivm.nl/documenten/bijlage-bij-rivm-brief-aan-iltindicatieve-drinkwaterrichtwaarde-trifluorazijnzuur-tfa ECHA REACH Dossier (2024) Han Wistar Rabbits embryo-fetal developmental toxicity <180 mg/kg/day multiple folded retina and absent aqueous/vitreous humor were above the … historical control data range Rategory 1B: Presumed human reproductive toxicant TFA able to become part of the lipids and biomolecules inside microbes …. no follow-up since 1999 If TFA covalently bonded with lipids, membranes, biomolecules, etc. they would ultimately be degraded to TFA… again Toxicity to aquatic ecosystems Aquatic toxicity of TFA •No observable effect concentration (NOEC) of 120 µg/L for Raphidocelis subcapitata –(Solvay data reported in Berends et al. 1999, USEEP ECOTOX). Used to derive a PNEC of 0.12 to 12 µg/L •Ignored as an outlier in some reports, but appears reproducible •ECHA REACH uses a ErC10 of 5600 µg/L based on an algae growth study, PNEC of 560 µg/L •Aquatic Concentrations exceeded in TFA hotspots and an increasing number of freshwater environments •All aquatic toxicity data for TFA is days to months, not years/lifetimes: reason to treat data with precaution Berends, A. G.; Boutonnet, J. C.; De Rooij, C. G.; Thompson, R.S. Toxicity of Trifluoroacetate to Aquatic Organisms. Environ. Toxicol.Chem. 1999, 18 (5), 1053−1059. Aquatic algae / microbes Toxicity to soil and terrestrial systems Chen et al. Environ. Sci. Technol.2018,52 (15), 8263–8271 •ECHA REACH dossier: long term No observable effect concentration (NOEC) 0.83 mg/kg soil (plant shoot growth) •TFA readily bioaccumulates in plants/shoots from soil •Effects on the soil pH, microbial respiration, bacterial abundance and litter decomposition were reported at TFA concentrations in soil in hotspots (0.0013–2.4 mg/kgdw), above this problems related to TFA acidity can occur. •Soil concentrations at TFA hotspots already exceed these concentrations which decrease soil quality •Little long exposure studies on terrestrial and agricultural systems Soils / terrestrial ecosystems TFA affecting soil health Jan Kopřiva Link to neurotoxicity with TFA-binding to proteins (differently than acetic acid) Pesticides and Pharmaceuticals •Biodegradable, non-fluorinated drugs an active area of «green pharmacy» innovation •Evaluate switching to PFAS free alternatives when recommending medications Provide tools for industry to find where and in what it is using PFAS https://pfas.chemsec.org/ The rap battle against PFAS https://www.youtube.com/watch?v=1q06fUMT_U4 PFAS production and products ZeroPM alternative assessment database •Find alternative for PFAS based on chemical function, end-use function, and function as a service https://zeropm.eu/alternative-assessment-database/ PFAS production and products Effective labelling what products make TFA Ellise Suffill, ZeroPM pieces #17 -Expert & non-expert perceptions on PFAS & essentiality in everyday products. https://zenodo.org/records/10628255 PFAS production and products We have the tools now to transition away from TFA, to stabilize exposure All you need is love and: Transition to PFAS and TFA free alternatives, start with TFA precursors produced in greatest volume Classify and label TFA as a PFAS, and integrate in PFAS reduction strategy (national and business) Remove TFA from active emission sources (industry effluent), ideally via the polluter pays principle Solutions 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://pubs.acs.org/doi/10.1021/acs.est.4c06189 Contact: [email protected]