Preprints
https://doi.org/10.5194/egusphere-2025-4824
© Author(s) 2025. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/egusphere-2025-4824
© Author(s) 2025. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
07 Oct 2025
| 07 Oct 2025
Status: this preprint is open for discussion and under review for Atmospheric Chemistry and Physics (ACP).
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
Abstract. Atmospheric observations of the widely used hydrofluoroolefins (HFOs) 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) are reported from the Advanced Global Atmospheric Gases Experiment (AGAGE) network. Since 2011, 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. For HFO-1234yf and HFO-1234ze(E) winter peak mole fractions in background northern hemisphere air have grown from 0.03 ppt (picomol mol-1, parts-per-trillion in dry air) in the mid-2010s to 0.25 ppt in 2024, while the atmospherically more stable HCFO-1233zd(E) showed an increase from 0.06 ppt to 0.45 ppt. This suggests increasing usage of these haloolefins to replace hydrofluorocarbons (HFCs), which are regulated for phase-down over the next decades. Using European observations and the inverse modeling frameworks InTEM, ELRIS, and RHIME we determine emission trends and regional distribution. For Northwest Europe, emissions of HFO-1234yf increased steadily and rapidly from <0.1 Gg yr-1 in 2014 to 1.50 Gg yr-1 by 2023, presumably due to its introduction in the mobile air conditioning and refrigeration sectors. HFO-1234ze(E) emissions were low during 2014–2017, followed by a rapid increase in 2018/2019, potentially due its introduction as aerosol propellant, after which they increased more slowly to 0.96 Gg yr-1 by 2023. HCFO-1233zd(E) emissions are derived from 2017 onwards, showing a steady increase from 0.2 Gg yr-1 to 1.0 Gg yr-1 in 2023.
How to cite. Vollmer, M. K., Pitt, J. R., Young, D., Henne, S., Mitrevski, B., Mühle, J., Ganesan, A., Arduini, J., Manning, A. J., Wagenhäuser, T., Redington, A. L., Murphy, B., Gluckmann, R., Stanley, K. M., Krummel, P. B., Lunder, C. R., Yun, J., Rust, D., Wenger, A., Guillevic, M., Kim, J., Wang, R. H. J., Rhee, T. S., Constantin, L., Frumau, A., Harth, C. M., Salameh, P. K., Hermansen, O., Engel, A., O'Doherty, S., Park, S., Maione, M., Fraser, P. J., Prinn, R. G., Weiss, R. F., and Reimann, S.: 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, EGUsphere [preprint], https://doi.org/10.5194/egusphere-2025-4824, 2025.
Publisher's note: Copernicus Publications remains neutral with regard to jurisdictional claims made in the text, published maps, institutional affiliations, or any other geographical representation in this paper. While Copernicus Publications makes every effort to include appropriate place names, the final responsibility lies with the authors. Views expressed in the text are those of the authors and do not necessarily reflect the views of the publisher.
Download & links
- Preprint
(17400 KB) - Metadata XML
-
Supplement
(12 KB) - BibTeX
- EndNote
Status: open (extended)
Comment types: AC – author | RC – referee | CC – community | EC – editor | CEC – chief editor
| : Report abuse
- RC1: 'Comment on egusphere-2025-4824', Isaac Vimont, 24 Nov 2025 reply
Viewed
Total article views: 413 (including HTML, PDF, and XML)
Cumulative views and downloads
(calculated since 07 Oct 2025)
| HTML | XML | Total | Supplement | BibTeX | EndNote | |
|---|---|---|---|---|---|---|
| 299 | 93 | 21 | 413 | 26 | 16 | 16 |
- HTML: 299
- PDF: 93
- XML: 21
- Total: 413
- Supplement: 26
- BibTeX: 16
- EndNote: 16
Viewed (geographical distribution)
Total article views: 410 (including HTML, PDF, and XML)
Thereof 410 with geography defined
and 0 with unknown origin.
| Country | # | Views | % |
|---|
| Total: | 0 |
| HTML: | 0 |
| PDF: | 0 |
| XML: | 0 |
- 1
1
Latest update: 06 Dec 2025
Laboratory for Air Pollution / Environmental Technology, Empa, Swiss Federal Laboratories for Materials Science and Technology, Überlandstrasse 129, 8600 Dübendorf, Switzerland
Joseph R. Pitt
Atmospheric Chemistry Research Group, School of Chemistry, University of Bristol, Bristol, UK
Dickon Young
Atmospheric Chemistry Research Group, School of Chemistry, University of Bristol, Bristol, UK
Stephan Henne
Laboratory for Air Pollution / Environmental Technology, Empa, Swiss Federal Laboratories for Materials Science and Technology, Überlandstrasse 129, 8600 Dübendorf, Switzerland
Blagoj Mitrevski
CSIRO Environment, Aspendale, Victoria, Australia
Jens Mühle
Scripps Institution of Oceanography, University of California San Diego, La Jolla, California, USA
Anita Ganesan
School of Geographical Science, University of Bristol, Bristol, UK
Jgor Arduini
Department of Pure and Applied Sciences, University of Urbino, Urbino, Italy
Institute of Atmospheric Sciences and Climate, Italian National Research Council, Bologna, Italy
Alistair J. Manning
Atmospheric Chemistry Research Group, School of Chemistry, University of Bristol, Bristol, UK
Met Office Hadley Centre, Exeter EX1 3PB, UK
Thomas Wagenhäuser
Institute for Atmospheric and Environmental Sciences, Goethe University, Frankfurt am Main, Germany
Alison L. Redington
Met Office Hadley Centre, Exeter EX1 3PB, UK
Brendan Murphy
Atmospheric Chemistry Research Group, School of Chemistry, University of Bristol, Bristol, UK
Ray Gluckmann
Gluckman Consulting, Cobham, Surrey, KT11 2JH, UK
Kieran M. Stanley
Atmospheric Chemistry Research Group, School of Chemistry, University of Bristol, Bristol, UK
Paul B. Krummel
CSIRO Environment, Aspendale, Victoria, Australia
Chris R. Lunder
NILU, Kjeller, Norway
Jaegeun Yun
School of Earth System Sciences, Kyungpook National University, South Korea
Dominique Rust
Atmospheric Chemistry Research Group, School of Chemistry, University of Bristol, Bristol, UK
Angelina Wenger
Atmospheric Chemistry Research Group, School of Chemistry, University of Bristol, Bristol, UK
Myriam Guillevic
Federal Office for the Environment FOEN, Bern, Switzerland
Jooil Kim
Scripps Institution of Oceanography, University of California San Diego, La Jolla, California, USA
Ray H. J. Wang
School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, Georgia, USA
Tae Siek Rhee
Korea Polar Research Institute, KIOST, Incheon, South Korea
Lionel Constantin
Laboratory for Air Pollution / Environmental Technology, Empa, Swiss Federal Laboratories for Materials Science and Technology, Überlandstrasse 129, 8600 Dübendorf, Switzerland
Arnoud Frumau
Department of Environmental Modelling, Sensing and Analysis, TNO, Netherlands Organisation for Applied Scientific Research, Petten, The Netherlands
Christina M. Harth
Scripps Institution of Oceanography, University of California San Diego, La Jolla, California, USA
Peter K. Salameh
GC Soft Inc., Carlsbad, CA, USA
Ove Hermansen
NILU, Kjeller, Norway
Andreas Engel
Institute for Atmospheric and Environmental Sciences, Goethe University, Frankfurt am Main, Germany
Simon O'Doherty
Atmospheric Chemistry Research Group, School of Chemistry, University of Bristol, Bristol, UK
Sunyoung Park
School of Earth System Sciences, Kyungpook National University, South Korea
Michela Maione
Department of Pure and Applied Sciences, University of Urbino, Urbino, Italy
Institute of Atmospheric Sciences and Climate, Italian National Research Council, Bologna, Italy
Paul J. Fraser
CSIRO Environment, Aspendale, Victoria, Australia
Ronald G. Prinn
Center for Global Change Science, Massachusetts Institute of Technology, Cambridge, Massachusetts, USA
Ray F. Weiss
Scripps Institution of Oceanography, University of California San Diego, La Jolla, California, USA
Stefan Reimann
Laboratory for Air Pollution / Environmental Technology, Empa, Swiss Federal Laboratories for Materials Science and Technology, Überlandstrasse 129, 8600 Dübendorf, Switzerland
Short summary
We provide atmospheric measurements of halogenated olefins from the Advanced Global Atmospheric Gases Experiments and we calculate NorthWest European Emissions.
We provide atmospheric measurements of halogenated olefins from the Advanced Global Atmospheric...
General Comments
“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” is an overview of measurements from the AGAGE network of 3 key haloolefins that are increasingly used in foam blowing and refrigeration, heating, and air-conditioning. The authors provide a nice overview of the global measurements, and provide more detailed analysis and emissions estimates for north western Europe. Additionally this paper easily meets every requirement set forth by ACP for publication in their journal.
This paper is excellent, and I have no major comments for the authors to address. I would like to thank the authors for providing such a well-written and thorough manuscript, it was a pleasure to read and review. This is a welcome change from many of the recent papers on halocarbons that I am asked to review. I further appreciate that the authors have taken the time to completely describe their calibration and uncertainty estimates (save for one small detail that I mention below). This is so often overlooked in manuscripts these days, and I found it a welcome change.
I did not find any issue with any of the modeling methods or results, however, the details of the models are outside my area of expertise and therefore I am not properly qualified to provide in-depth review of that portion of the text. It is a shame that these compounds are too short-lived for estimates of global emissions using traditional box modeling methods, as it would be nice to have global estimations of these species going forward as they are used increasingly throughout the world. However, an analysis of global emissions using more complex, full chemistry global models is outside the scope of this paper (indeed, likely a paper on its own).
In my opinion, the paper is nearly ready to publish in ACP. I have included a small number of minor, admittedly nit-picky, comments below, easily addressed, but overall, the paper is excellent and I look forward to its imminent publication.
Specific Comments
Line 35: This part of the sentence (...currently an intense debate…) is ambiguous (is the debate about banning PFA’s or about adding HFO’s to the ban?). To me, it doesn’t add much to the paper nor the point being made in the paragraph. Suggest:
“Haloolefins are also within the scope of the definition of the very stable anthropogenic per- and polyfluoroalkyl substances (PFAS). In January 2023, authorities from Denmark, Germany, the Netherlands, Norway, and Sweden submitted a REACH (Registration, Evaluation, Authorisation and Restriction of Chemicals) dossier for a restriction proposal for PFAS in the EU to the European Chemicals Agency (ECHA, European Chemicals Agency, 2024) which suggests a wide-ranging ban of PFAS from usage in many applications. At the time of publication, this dossier is still being considered by the ECHA.”
Line 51: This paragraph seems out of place. We are 4 paragraphs into the introduction and only now are the three species listed and their uses explained. I suggest moving this up to be the second paragraph (currently the second paragraph starts at line 30). This would help clarify several points being made in the current second and third paragraphs.
Line 56: “...and also difficult to reconstruct the temporal changes in regulations and applications in various parts of the world”. To me, this sentence is unclear. What regulations do you refer to here? Above you have stated that haloolefins are up for consideration for regulation in the EU and that the MP does not restrict their use at this time. Or is this meant to say that it will be difficult in the future?
Section 2.2: Monte Cimone has 5 years of data with a non-Medusa system, yet there is no description of any difference in measurement precisions for the three compounds, or detectability. From what I can see in the data presented here, there seems to be no change in the measurement quality, nor the detection limits, when the Monte Cimone site was switched to the Medusa system, which is excellent.
However, though this system is described in Maione et al., 2013), I suggest the authors provide a little bit more information on the comparability of these two instruments. Given the ~14 months of overlap, this may be easy, and can be as little as to say that the measurement quality is comparable (assuming that it is), or a short mention in Section 2.4 if there is any small difference.
Section 2.4: What are the uncertainties for clean air samples? Unless misread here, I see an excellent detailing of polluted sample uncertainty, but no mention of unpolluted background air uncertainties? I would expect that the uncertainty will increase somewhat as the chromatographic peak approaches the detection limit.
Line 338: “...large magnitudes of pollution…” is awkward. Suggest changing to “...large enhancements relative to background…”
Sections 3.1.1 and 3.1.2: I have some minor skepticism of the conclusions drawn in these two sections relating to the slower adoption of HFO’s in the region of influence for the Gosan station relative to the European stations, particularly with respect to 134a. The Gosan Station has significant influence from both the DPRK, the Republic of Korea, and Eastern China. Both the Korean and Chinese automobile industries have exploded in the last 10 years, with Korea’s beginning even before this. Though my experience with specific vehicles is quite limited, both modern Chinese and Korean vehicles are coming with haloolefin refrigerants, and have been for some time. Despite the DPRK, China, and the Republic of Korea being A5 countries and thus having longer phase down times, both the Korean and Chinese automobile manufacturers are targeting non-A5 countries for sales, including the US, Europe, and Australia. They would be prevented from selling vehicles in these regions with 134a, and from a manufacturing perspective, it is difficult to see how they would tool their manufacturing plants differently depending on whether the vehicle was to be sold domestically or internationally.
If we assume the conclusions drawn here are true, it would be good to discuss why the vehicle fleets in China and Korea would be expected to be largely running 134a despite their new vehicles being produced with HFO-1234yf. Unlike the US, Europe, Australia, etc… where the vehicle fleets might be expected to contain significant numbers of older vehicles (though from this paper it is clear that Europe's fleet is changing over), China’s fleet is likely quite a bit newer, as evidenced by their historically low, but rapidly increasing, vehicle ownership statistics (e.g. https://doi.org/10.1007/s11356-024-34344-0). I think the authors could expand a bit on this, as while their conclusions are certainly plausible, to me they have not addressed this additional factor which could run counter to their hypothesis.