the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Estimation of the atmospheric hydroxyl radical oxidative capacity using multiple hydrofluorocarbons (HFCs)
Stephen A. Montzka
Martin K. Vollmer
Jgor Arduini
Molly Crotwell
Paul Krummel
Chris Lunder
Jens Mühle
Simon O'Doherty
Ronald G. Prinn
Stefan Reimann
Isaac Vimont
Hsiang Wang
Ray F. Weiss
Dickon Young
Abstract. The hydroxyl radical (OH) largely determines the atmosphere’s oxidative capacity and, thus, the lifetimes of numerous trace gases, including methane (CH4). Hitherto, observation-based approaches for estimating the atmospheric oxidative capacity have primarily relied on using methyl chloroform (MCF), but as the atmospheric abundance of MCF has declined, the uncertainties associated with this method have increased. In this study, we examine the use of five hydrofluorocarbons (HFCs) (HFC-134a, HFC-152a, HFC-365mfc, HFC-245fa and HFC-32) in multi-species inversions, which assimilate three HFCs simultaneously, as an alternative method to estimate atmospheric OH. We find robust estimates of OH regardless of which combination of three HFCs are used in the inversions. Our results show that OH has remained fairly stable during our study period from 2004 to 2021, with variations of <2 % and no significant trend. Inversions including HFC-32 and HFC-152a (the shortest-lived species) indicate a small reduction in OH in 2020 (1.6 % ± 0.9 % relative to the mean over 2004–2021 and 0.6 ± 0.9 % lower than in 2019), but considering all inversions, the reduction was only 0.5 ± 1.1 % and OH was at a similar level to that in 2019.
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Rona L. Thompson et al.
Status: open (until 11 Oct 2023)
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RC1: 'Comment on egusphere-2023-1917', Anonymous Referee #1, 30 Sep 2023
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General Comments
This manuscript presents an inversion study of five HFCs (different combinations of three at a time) to infer global annual mean hydroxyl radical (OH) concentrations using a 12-box model. The inferred OH anomalies are compared against other estimates from past MCF and CTM-based analyses. Finally, the impact of the optimized OH on the growth rate and emissions of CH4 is derived from the same 12-box inversion relative to a Spivakovsky et al. climatology. The results suggest that variability in the annual OH anomaly is less than 2% with no trend over the period 2004-2021, that OH abundance in year 2020 was likely low but not significantly lower than in prior years (2018 especially), and that CH4 emissions using the optimized OH had a smaller increase than is inferred using climatology, though the difference is small.
Overall, this is a compelling study focused on an important topic. The global oxidizing capacity is a subject of much debate, and further observational constraints to quantify it are always needed. The methodology used is sound, and I see no shortcomings in what is presented. I point out in my comments an opportunity for expanded discussion and a couple small clarifications, but otherwise, I think the article is well-presented, is of interest to readers of ACP, and represents a significant advance beyond the use of MCF as the main observational proxy of OH.
Specific Comments
L39: Turner et al., PNAS, 2017 (https://doi.org/10.1073/pnas.1616020114) could be added to the list of MCF studies
L275: It would be informative to expand on the discussion of the “shortest lived species” a bit. It is stated earlier in the manuscript that the derived OH may be more sensitive to the shorter-lived species in the inversion. Wouldn’t it also make sense that, in the actual atmosphere, the shorter-lived species would adjust more quickly to either changes in emissions or variations in OH? This is not explicitly stated in the text, but since the authors separated out inversions that included the shorter-lived species (e.g., in Fig. 3), why not discuss the implications more?
Figure S1: For the lower row of panels in each set, I think it would help to indicate on the y-axis that this represents a difference (something like “HFC-32 Difference, AGAGE – NOAA (ppt)” or similar).
Technical Corrections
Figure S5: Should the caption state “ten inversions” rather than six?
Figure S6: Figure seems low resolution, e.g. when compared to Figure S5.
Citation: https://doi.org/10.5194/egusphere-2023-1917-RC1
Rona L. Thompson et al.
Rona L. Thompson et al.
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