Global Observations and European emissions of the halogenated olefins HFO-1234yf, HFO-1234ze(E), and HCFO-1233zd(E) from the AGAGE (Advanced Global Atmospheric Gases Experiment) network

Short Summary: Halogenated olefins (HFOs) are newly emerging compounds in the atmosphere. They are in reach of the definition of PFAS (Per- and polyfluoroalkyl substances) and some decay to the eternal chemical trifluoroacetate (TFA). We provide atmospheric measurements of three HFOs from the large Advanced Global Atmospheric Gases Experiment (AGAGE) network and estimate emissions for Northwest Europe for the first time. We find a quasi-ubiquitous presence in the atmosphere and rapidly increasing emissions.

Abstract: Hydrofluoroolefins (HFOs) are important synthetic compounds replacing other halocarbons in phase-down from usage (e.g., as refrigerants, propellants, foam blowing). Little is known about their atmospheric abundance, distribution and trends, nor about their emissons. Here, we report atmospheric observations of the widely used HFO-1234yf (2,3,3,3-tetrafluoroprop-1-ene), and HFO-1234ze(E) (E-1,3,3,3-tetrafluoroprop-1-ene), and the hydrochlorofluoroolefin (HCFO) HCFO-1233zd(E) (E-1-chloro-3,3,3-trifluoroprop-1-ene) observed as part of the Advanced Global Atmospheric Gases Experiment (AGAGE) network. 

Over the observational period 2011–2025, pollution events have grown in magnitude and frequency at sites which are influenced by regional emissions, while remote stations show first appearances of these substances. 

By 2024/2025 winter peak mole fractions in background northern hemisphere air have reached ∼ 0.25 ppt (picomol mol⁻¹, parts-per-trillion in dry air) for HFO-1234yf and HFO-1234ze(E) and ∼ 0.45 ppt for HCFO-1233zd(E). Using European observations and the inverse modeling frameworks InTEM, ELRIS, and RHIME we determine emission trends and regional distributions. For Northwest Europe, emissions of HFO-1234yf increased steadily and rapidly from <0.1 Gg yr⁻¹ in 2014 to 1.50 [1.23–1.74, range of 16–84 percentile] Gg yr⁻¹ by 2023, presumably due to its introduction in mobile air conditioning and stationary refrigeration. HFO-1234ze(E) emissions were low during 2014–2017, followed by a rapid increase in 2018/2019, potentially due its introduction as an aerosol propellant, after which they increased more slowly to 0.96 [0.82–1.13] Gg yr⁻¹ by 2023. HCFO-1233zd(E) emissions are derived from 2017 onward, showing a steady increase from 0.15 [0.07–0.23] to 1.04 [0.93–1.15] Gg yr⁻¹ in 2023.