A representative of Deutsche Umwelthilfe/DUH (Environmental Action Germany) has called for an immediate stop to the growing emissions of f-gas byproduct trifluoracetic acid (TFA) given its infiltration throughout the global environment and its “real risk” to human health.
The call came from Christine Luetzkendorf, Policy Advisor on Fluorinated Greenhouse Gases at DUH, during a PFAS panel discussion on November 26 at the ATMOsphere (ATMO) Europe Summit 2024 on natural refrigerant-based cooling and heating, held in Prague, Czech Republic, November 25–26.
The panel discussion, co-moderated by Michael Kauffeld of Karlsruhe University and ATMOsphere CEO Marc Chasserot, also included Jonatan Kleimark, Senior Chemicals and Business Advisor at ChemSec, and Cinzia Verzeletti, Senior Campaigner at ATMOsphere. The Summit was organized by ATMOsphere, publisher of NaturalRefrigerants.com.
Kauffeld, a Professor at the Karlsruhe University of Applied Sciences, Institute of Refrigeration, Air-Conditioning and Environmental Engineering in Germany, preceded the PFAS panel with a keynote address titled “PFAS – a growing concern in the HVACR industry.”
“We need to stop TFA emissions as of right now,” said Luetzkendorf. “Yes, there are still some uncertainties about the full toxicity data. But we have sufficient data. We know enough to conclude that TFA is a very real risk to humans and to the environment and that TFA is actually a planetary boundary threat.” She referred to a recently published study stating that TFA should be considered a “planetary boundary threat” because of its increasing planetary-scale exposure, where potentially irreversible disruptive impacts on vital earth system processes could occur.
Action is needed on a global basis, Luetzkendorf said, including “policy mechanisms, industry initiatives, innovation actions and investor actions to really reduce TFA emissions and to protect future generations.”
Verzeletti of ATMOsphere noted that it is incumbent on the EU to regulate PFAS, including f-gases and TFA, because of “the precautionary principle of environmental law,” which is enshrined in the Treaty on the Functioning of the European Union (TFEU). “Even if scientific certainty is not there yet, we have sufficient proof that creates this need for action,” she said.
Sources of TFA
Several HFOs and HFC-134a degrade to TFA when they leak into the atmosphere, but the most prominent is HFO-1234yf, used globally in millions of car air-conditioning systems and in commercial refrigerant blends; within a few weeks it undergoes 100% transformation to TFA, which then comes down to Earth in rainfall. F-gases are regarded as the primary source of environmental TFA, noted Luetzkendorf, but other agents that create TFA in the environment include byproducts of pesticides, pharmaceuticals, fluoropolymers and other PFAS, as well as the direct release of industrially produced TFA and TFA emitted from wastewater treatment plants and landfills.
Because of its mobility in water and persistence, “TFA is found everywhere – it’s the most abundant PFAS around,” she said. “It’s in every single water body. It’s in plants and wine and beer, in our blood. It can pass our brain blood barrier. It can pass through our placenta, if we have one.”
While the chemical industry claims that TFA can be produced in nature, “there’s actually insufficient evidence on the natural occurrence of TFA,” said Luetzkendorf. “And even if there is some wild underwater volcano somewhere that produces a little bit of TFA, this has nothing to do with the concentration that we see in our waters on our earth right now.”
The other dilemma with TFA is the difficulty of removing it from water at scale, Luetzkendorf noted. The primary method, reverse osmosis is extremely expensive and energy intensive, results in 50% water loss and leaves a toxic residue. However, researchers from the University of Illinois, Urbana-Champaign have recently developed an electrochemical process designed to economically remove up to 86% of TFA) as well as long-chain PFAS from water intended for human consumption.
Forever chemicals
TFA and its f-gas precursors are considered PFAS (per-and polyfluoroalkyl substances) by the EU and scientists worldwide because they have at least one fully fluorinated carbon atom. PFAS, also known as “forever chemicals” for their extreme persistence in nature, encompass more than 14,000 synthetic substances that are used in many common consumer and industrial products. PFAS that contain eight carbon atoms, such as PFOA and PFOS, have been linked to serious health problems, including kidney and testicular cancer.
The European Chemicals Agency (ECHA), an EU body, is considering a proposal to regulate PFAS as a category, including f-gases and TFA, under REACH (Registration, Evaluation, Authorisation and Restriction of Chemicals), the EU’s chemicals regulation. Also in the EU, a new organization, the Coalition for PFAS Free Cooling & Heating, has been launched, with ATMOsphere, publisher of NaturalRefrigerants.com, as a founding member. The organization will be dedicated to promoting natural refrigerants as alternatives to harmful PFAS in cooling and heating systems and supporting ambitious European PFAS legislation.
Exposure to TFA, an ultrashort-chain PFAS with two carbon atoms, has not been conclusively associated with health effects, but the German government this year proposed to the EU linking TFA to reproductive toxicity based on evidence of embryo-fetal developmental toxicity in rabbits (in particular, malformation of the eyes in offspring), and TFA has been connected to liver dysfunction in rats. Germany has also proposed categorizing TFA in the EU as persistent, mobile and toxic (PMT) and very persistent and very mobile (vPvM).
Some reports, such as UNEP’s Environmental Effects Assessment Panel (EEAP) 2022 assessment, say that TFA is not bioaccumulative. But Luetzkendorf pointed out that there are studies showing that TFA is bioaccumulated in plants and incorporated in the proteins of plants’ cell walls. “it’s really important that this research gets picked up again so we find out more,” she said.
“TFA is found everywhere – it’s the most abundant PFAS around.”
Christine Luetzkendorf, Policy Advisor on Fluorinated Greenhouse Gases at DUH
German authorities, noted Luetzkendorf, have proposed to ECHA that it should reclassify TFA as “reprotoxic,” PMT and vPvM under the EU’s classification, labeling and packaging (CLP) regulation. The regulation requires manufacturers, importers or downstream users of substances or mixtures to classify, label and package their hazardous chemicals appropriately before placing them on the market so that the hazards are clearly communicated to workers and consumers. The CLP regulation also calls for harmonized classification and labelling (CLH) into different hazard classes pertaining to physical threats like flammability, health issues and environmental concerns. TFA is already classified as harmful if inhaled, causing skin corrosion and harmful to aquatic life.
ECHA is doing an “accordance check” of Germany’s proposal, which may be completed “in a matter of weeks,” said Luetzkendorf. The proposal would then be made public and will have a consultation phase of 60 days during which stakeholders can react. Based on the consultation, ECHA’s Committee on Risk Assessment (RAC) will adopt an opinion, after which it goes to the European Commission, which has a final vote on whether to approve the reclassifications.
The EU is not expected to finalize its universal PFAS and CLP regulations for several years, but Luetzkendorf stressed that the HVAC&R industry does not need to wait for the regulations to be enacted because of the current availability of natural refrigerant alternatives to HFOs. “So let’s do that transition right now,” she said, adding that the industry still has to overcome “ignorance” and misinformation about natural refrigerants and TFA.
The chemical industry addressed the environmental deposition of TFA in an October 2021 study funded by the Global Forum for Advanced Climate Technologies (globalFACT), which represents f-gas producers Chemours, Honeywell, Arkema and Koura. The study concluded that “with the current knowledge of the effects of TFA on humans and ecosystems, the projected emissions through 2040 would not be detrimental.” But the study also acknowledged that “the major uncertainty in the knowledge of the TFA concentrations and their spatial distributions is due to uncertainties in the future projected emissions.”
Talking to policymakers
Another PFAS panelist, Kleimark of ChemSec, provided an update on ECHA’s consideration of the proposal to restrict PFAS as a “universal” category, including most f-gases and TFA. ChemSec, a Swedish environmental NGO, is an observer in ECHA’s Committee on Socio-Economic Analysis (SEAC) and has recently been part of RAC – the committees engaged in evaluating the PFAS restriction proposal.
The universal PFAS regulation would restrict the manufacture, placing on the market and use of PFAS. It covers over 10,000 substances used in more than 14 sectors but excludes biocides, pharmaceuticals and plant protection products, which are addressed in other regulations. PFAS restrictions have been proposed that would include either a ban or a ban with derogations (time-limited exemptions) where alternatives are not yet available. Recently, restriction options other than a ban have been proposed.
In regard to refrigerants, the following ban derogations have been proposed:
- For 13.5 years after the regulation enters into force for refrigerants used in maintenance and refilling of existing HVAC&R equipment put on the market up to 18 months after the regulation enters into force.
- For 6.5 years after the regulation enters into force for refrigerants used in mobile air-conditioning systems in combustion engine vehicles with mechanical compressors.
- For 6.5 years after the regulation enters into force for refrigerants used in mobile air-conditioning in transportation vehicles for military applications.
However, Kleimark expects that when the discussions come to the f-gases in 2025, “the industry will propose a large set of [other] derogations for this use or this application.” Derogations are granted if there are no available and viable alternatives to f-gases, but with the availability of natural refrigerant-based systems, “we have a set of alternatives,” he said. “We have already companies that have phased out of f-gases. So a lot of things are happening due to the upcoming legislation.”
Kleimark believes there is a lot of value in talking to policymakers about the availability of f-gas alternatives over the next year during the SEAC public consultation. The use of natural refrigerants “is still not obvious to the people that are doing the work with the proposal right now, [nor to] the policymakers or the member states.”
After committees are finished with their evaluations, their opinions will be submitted to the European Commission. The Commission will write its proposal, which will be decided upon by the member states. “We probably won’t have a decision until maybe 2028, or even later than that,” said Kleimark. But I would like to stress that it’s important that we have a comprehensive regulation in order to beat the PFAS crisis. And that’s why it will take some time.”
Advocating for PFAS Free Cooling & Heating
Verzeletti of ATMOsphere provided information about the new Coalition for PFAS Free Cooling & Heating, whose initial members include ATMOsphere, Fenagy, Secon, Teko, Konvekta, Refra and Güntner. The coalition is open to other companies focused on the use of PFAS-free natural refrigerants – CO2 (R744), ammonia (R717), hydrocarbons, air and water, all found in nature – in HVAC&R applications.
The Coalition’s mission, she said, is to “advocate for an ambitious PFAS restriction regulating the use of HFOs in applications where commercially available natural regional alternatives exist” as a counterweight to the lobbying of the chemical industry.
To that end, said Verzeletti, the Coalition will be “providing facts and strong evidence” to the SEAC in ECHA as it evaluates regulations on f-gases and TFA. It will also be working with two universities – Karlsruhe University and OST (Eastern Swiss University of Applied Sciences) – which have devised a methodology to calculate the PFAS risk in end products in the HVAC&R industry.
