First ground-based Fourier transform infrared (FTIR) spectrometer observations of HFC-23 at Rikubetsu, Japan, and Syowa Station, Antarctica
Authors: Takeda Masanori , Nakajima Hideaki , Murata Isao , Nagahama Tomoo , Morino Isamu , Toon Geoffrey C. , Weiss Ray F. , Mühle Jens , Krummel Paul B. , Fraser Paul J. , Wang Hsiang-Jui 
Published: September 2021

Abstract. We have developed a procedure for retrieving atmospheric abundances of HFC-23 (CHF3) with a ground-based Fourier transform infrared (FTIR)
spectrometer and analyzed the spectra observed at Rikubetsu, Japan (43.5∘ N, 143.8∘ E), and at Syowa Station, Antarctica
(69.0∘ S, 39.6∘ E). The FTIR retrievals were carried out with the SFIT4 retrieval program, and the two spectral windows of
1138.5–1148.0 cm−1 and 1154.0–1160.0 cm−1 in the overlapping ν2 and ν5 vibrational–rotational transition
bands of HFC-23 were used to avoid strong H2O absorption features. We considered O3, N2O, CH4,
H2O, HDO, CFC-12 (CCl2F2), HCFC-22 (CHClF2), peroxyacetyl nitrate (PAN) (CH3C(O)OONO2), HCFC-141b
(CH3CCl2F), and HCFC-142b (CH3CClF2) to be interfering species. Vertical profiles of H2O, HDO, and
CH4 are preliminarily retrieved with other independent spectral windows because these profiles may induce large uncertainties in the
HFC-23 retrieval. Each HFC-23 retrieval has only one piece of vertical information with sensitivity to HFC-23 in the
troposphere and the lower stratosphere. Retrieval errors mainly arise from the systematic uncertainties of the spectroscopic parameters used to
obtain HFC-23, H2O, HDO, and CH4 abundances. For comparison between FTIR-retrieved HFC-23 total columns and
surface dry-air mole fractions provided by AGAGE (Advanced Global Atmospheric Gases Experiment), FTIR-retrieved HFC-23 dry-air
column-averaged mole fractions (XHFC-23) were calculated. The FTIR-retrieved XHFC-23 values at Rikubetsu and Syowa Station have
negative biases of −15 % to −20 % and −25 % compared to the AGAGE datasets, respectively. These negative biases might mainly come from
systematic uncertainties of HFC-23 spectroscopic parameters. The trend of the FTIR-retrieved XHFC-23 data at Rikubetsu was
derived for December to February (DJF) observations, which are considered to represent the background values when an air mass reaching Rikubetsu has the
least influence by transport of HFC-23 emissions from nearby countries. The DJF trend of Rikubetsu over the 1997–2009 period is
0.810 ± 0.093 ppt yr−1 (ppt: parts per trillion), which is in good agreement with the trend derived from the annual global mean
datasets of the AGAGE 12-box model for the same period (0.820 ± 0.013 ppt yr−1). The DJF trend of Rikubetsu over the 2008–2019
period is 0.928 ± 0.108 ppt yr−1, which is consistent with the trend in the AGAGE in situ measurements at Trinidad Head
(41.1∘ N, 124.2∘ W) for the same period (0.994 ± 0.001 ppt yr−1). The trend of the FTIR-retrieved
XHFC-23 data at Syowa Station over the 2007–2016 period is 0.819 ± 0.071 ppt yr−1, which is consistent with that
derived from the AGAGE in situ measurements at Cape Grim (40.7∘ S, 144.7∘ E) for the same period
(0.874 ± 0.002 ppt yr−1). Although there are systematic biases in the FTIR-retrieved XHFC-23 at both sites, these
results indicate that ground-based FTIR observations have the capability to monitor the long-term trend of atmospheric HFC-23. If this FTIR
measurement technique were extended to other Network for the Detection of Atmospheric Composition Change (NDACC) ground-based FTIR sites around world, the measurements reported from these sites would complement
the global AGAGE observations by filling spatial and temporal gaps and may lead to improved insights about changes in regional and global emissions
of HFC-23 and its role in global warming.