Articles | Volume 25, issue 19
https://doi.org/10.5194/acp-25-11895-2025
© 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/acp-25-11895-2025
© Author(s) 2025. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
02 Oct 2025
Research article |
| 02 Oct 2025
| 02 Oct 2025
Stratospheric δ13CO2 observed over Japan and its governing processes
Satoshi Sugawara
CORRESPONDING AUTHOR
Faculty of Education, Miyagi University of Education, Sendai 980-0845, Japan
Shinji Morimoto
Center for Atmospheric and Oceanic Studies, Tohoku University, Sendai 980-8578, Japan
Shigeyuki Ishidoya
National Institute of Advanced Industrial Science and Technology (AIST), Tsukuba 305-8569, Japan
Taku Umezawa
National Institute for Environmental Studies, Tsukuba 305-8506, Japan
Center for Atmospheric and Oceanic Studies, Tohoku University, Sendai 980-8578, Japan
Shuji Aoki
Center for Atmospheric and Oceanic Studies, Tohoku University, Sendai 980-8578, Japan
Takakiyo Nakazawa
Center for Atmospheric and Oceanic Studies, Tohoku University, Sendai 980-8578, Japan
Sakae Toyoda
School of Materials and Chemical Technology, Institute of Science Tokyo, Yokohama 226-8501, Japan
Kentaro Ishijima
Meteorological Research Institute, Japan Meteorological Agency, Tsukuba 305-0052, Japan
Daisuke Goto
National Institute of Polar Research, Tachikawa 190-8518, Japan
Hideyuki Honda
Center for Atmospheric and Oceanic Studies, Tohoku University, Sendai 980-8578, Japan
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Satoshi Sugawara, Ikumi Oyabu, Kenji Kawamura, Shigeyuki Ishidoya, Shinji Morimoto, Shuji Aoki, Takakiyo Nakazawa, Sakae Toyoda, and Hideyuki Honda
EGUsphere, https://doi.org/10.5194/egusphere-2025-2916, https://doi.org/10.5194/egusphere-2025-2916, 2025
This preprint is open for discussion and under review for Atmospheric Chemistry and Physics (ACP).
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Stratospheric air samples have been collected using balloon-borne cryogenic samplers over Japan and analyzed for the isotopic and elemental ratios of noble gases. We report the results of the first study on the vertical changes of Kr, Xe, and Ne in the stratosphere. The observed results suggest that not only gravitational separation but also kinetic fractionation occurred in the stratosphere. The kinetic fractionations would be an additional tool to diagnose stratospheric transport processes.
Shigeyuki Ishidoya, Satoshi Sugawara, and Atsushi Okazaki
Atmos. Chem. Phys., 25, 1965–1987, https://doi.org/10.5194/acp-25-1965-2025, https://doi.org/10.5194/acp-25-1965-2025, 2025
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The 18O/16O ratio of atmospheric oxygen, δatm(18O), is higher than that of ocean water due to isotopic effects during biospheric activities. This is known as the Dole–Morita effect, and its millennial-scale variations are recorded in ice cores. However, small variations of δatm(18O) in the present day have never been detected so far. This paper presents the first observations of diurnal, seasonal, and secular variations in δatm(18O) and applies them to evaluate oxygen, carbon, and water cycles.
Taku Umezawa, Satoshi Sugawara, Kenji Kawamura, Ikumi Oyabu, Stephen J. Andrews, Takuya Saito, Shuji Aoki, and Takakiyo Nakazawa
Atmos. Chem. Phys., 22, 6899–6917, https://doi.org/10.5194/acp-22-6899-2022, https://doi.org/10.5194/acp-22-6899-2022, 2022
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Greenhouse gas methane in the Arctic atmosphere has not been accurately reported for 1900–1980 from either direct observations or ice core reconstructions. By using trace gas data from firn (compacted snow layers above ice sheet), air samples at two Greenland sites, and a firn air transport model, this study suggests a likely range of the Arctic methane reconstruction for the 20th century. Atmospheric scenarios from two previous studies are also evaluated for consistency with the firn data sets.
Shigeyuki Ishidoya, Satoshi Sugawara, Yasunori Tohjima, Daisuke Goto, Kentaro Ishijima, Yosuke Niwa, Nobuyuki Aoki, and Shohei Murayama
Atmos. Chem. Phys., 21, 1357–1373, https://doi.org/10.5194/acp-21-1357-2021, https://doi.org/10.5194/acp-21-1357-2021, 2021
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The surface Ar / N2 ratio showed not only secular increasing trends, but also interannual variations in phase with the global ocean heat content (OHC). Sensitivity test by using a two-dimensional model indicated that the secular trend in the Ar / N2 ratio is modified by the gravitational separation in the stratosphere. The analytical results imply that the surface Ar/N2 ratio is an important tracer for detecting spatiotemporally integrated changes in OHC and stratospheric circulation.
Ikumi Oyabu, Kenji Kawamura, Kyotaro Kitamura, Remi Dallmayr, Akihiro Kitamura, Chikako Sawada, Jeffrey P. Severinghaus, Ross Beaudette, Anaïs Orsi, Satoshi Sugawara, Shigeyuki Ishidoya, Dorthe Dahl-Jensen, Kumiko Goto-Azuma, Shuji Aoki, and Takakiyo Nakazawa
Atmos. Meas. Tech., 13, 6703–6731, https://doi.org/10.5194/amt-13-6703-2020, https://doi.org/10.5194/amt-13-6703-2020, 2020
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Air in polar ice cores provides information on past atmosphere and climate. We present a new method for simultaneously measuring eight gases (CH4, N2O and CO2 concentrations; isotopic ratios of N2 and O2; elemental ratios between N2, O2 and Ar; and total air content) from single ice-core samples with high precision.
Masahito Ueyama, Taku Umezawa, Yukio Terao, Mark Lunt, and James Lawrence France
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Methane (CH4) emissions were measured in the megacity of Osaka, Japan, using mobile and eddy covariance methods. The CH4 emissions were much higher than those reported in local inventories, with natural gas contributing up to 74 % of the emissions. Several CH4 sources not accounted for in current inventories were identified. These results emphasize the need for more comprehensive emissions tracking in urban areas to enhance climate change mitigation efforts.
Masahito Ueyama, Yuta Takao, Hiromi Yazawa, Makiko Tanaka, Hironori Yabuki, Tomo'omi Kumagai, Hiroki Iwata, Md. Abdul Awal, Mingyuan Du, Yoshinobu Harazono, Yoshiaki Hata, Takashi Hirano, Tsutom Hiura, Reiko Ide, Sachinobu Ishida, Mamoru Ishikawa, Kenzo Kitamura, Yuji Kominami, Shujiro Komiya, Ayumi Kotani, Yuta Inoue, Takashi Machimura, Kazuho Matsumoto, Yojiro Matsuura, Yasuko Mizoguchi, Shohei Murayama, Hirohiko Nagano, Taro Nakai, Tatsuro Nakaji, Ko Nakaya, Shinjiro Ohkubo, Takeshi Ohta, Keisuke Ono, Taku M. Saitoh, Ayaka Sakabe, Takanori Shimizu, Seiji Shimoda, Michiaki Sugita, Kentaro Takagi, Yoshiyuki Takahashi, Naoya Takamura, Satoru Takanashi, Takahiro Takimoto, Yukio Yasuda, Qinxue Wang, Jun Asanuma, Hideo Hasegawa, Tetsuya Hiyama, Yoshihiro Iijima, Shigeyuki Ishidoya, Masayuki Itoh, Tomomichi Kato, Hiroaki Kondo, Yoshiko Kosugi, Tomonori Kume, Takahisa Maeda, Shoji Matsuura, Trofim Maximov, Takafumi Miyama, Ryo Moriwaki, Hiroyuki Muraoka, Roman Petrov, Jun Suzuki, Shingo Taniguchi, and Kazuhito Ichii
Earth Syst. Sci. Data, 17, 3807–3833, https://doi.org/10.5194/essd-17-3807-2025, https://doi.org/10.5194/essd-17-3807-2025, 2025
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The JapanFlux2024 dataset, created through collaboration across Japan and East Asia, includes eddy covariance data from 83 sites spanning 683 site-years (1990–2023). This comprehensive dataset offers valuable insights into energy, water, and CO2 fluxes, supporting research on land–atmosphere interactions and process models; fosters global collaboration; and advances research in environmental science and regional climate dynamics.
Taku Umezawa, Yukio Terao, Masahito Ueyama, Satoshi Kameyama, Mark Lunt, and James Lawrence France
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To take effective mitigation actions, accurate understanding of methane emission characteristics in cities is important. We conducted atmospheric methane and ethane measurements using a vehicle in the world’s largest megacity, Tokyo, to identify locations and types of emissions and estimate their magnitudes. Waste sectors and fugitive natural gas emissions were found to be the major urban sources, and our data suggested need of improved accounting of natural gas related emissions.
Mizuo Kajino, Kentaro Ishijima, Joseph Ching, Kazuyo Yamaji, Rio Ishikawa, Tomoki Kajikawa, Tanbir Singh, Tomoki Nakayama, Yutaka Matsumi, Koyo Kojima, Taisei Machida, Takashi Maki, Prabir K. Patra, and Sachiko Hayashida
Atmos. Chem. Phys., 25, 7137–7160, https://doi.org/10.5194/acp-25-7137-2025, https://doi.org/10.5194/acp-25-7137-2025, 2025
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Air pollution in Delhi during the post-monsoon period is severe, and association with intensive crop residue burning (CRB) over Punjab state has attracted attention. However, the relationship has been unclear as the CRB emissions conventionally derived from satellites were underestimated due to clouds or thick smoke/haze over the region. We evaluated the impact of CRB on PM2.5 to be about 50 %, based on a combination of numerical modeling and an observation network using low-cost sensors we installed.
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This preprint is open for discussion and under review for Atmospheric Chemistry and Physics (ACP).
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Stratospheric air samples have been collected using balloon-borne cryogenic samplers over Japan and analyzed for the isotopic and elemental ratios of noble gases. We report the results of the first study on the vertical changes of Kr, Xe, and Ne in the stratosphere. The observed results suggest that not only gravitational separation but also kinetic fractionation occurred in the stratosphere. The kinetic fractionations would be an additional tool to diagnose stratospheric transport processes.
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In this study, offsets of CO2 values due to thermal diffusion effect were observed in the outflowing gas from cylinders finding that the CO2 mole fraction in a cylinder deviate by this effect as the pressure dropped. This result suggests that the deviation in the CO2 value in the cylinder is caused not only by the adsorption and desorption effects but also by the thermal diffusion fractionation effect.
Bibhasvata Dasgupta, Malika Menoud, Carina van der Veen, Ingeborg Levin, Cora Veidt, Heiko Moossen, Sylvia Englund Michel, Peter Sperlich, Shinji Morimoto, Ryo Fujita, Taku Umezawa, Stephen Matthew Platt, Christine Groot Zwaaftink, Cathrine Lund Myhre, Rebecca Fisher, David Lowry, Euan Nisbet, James France, Ceres Woolley Maisch, Gordon Brailsford, Rowena Moss, Daisuke Goto, Sudhanshu Pandey, Sander Houweling, Nicola Warwick, and Thomas Röckmann
EGUsphere, https://doi.org/10.5194/egusphere-2025-2439, https://doi.org/10.5194/egusphere-2025-2439, 2025
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We combined long-term methane mole fraction and isotope measurements from eight laboratories that sample high-latitude stations to compare, offset correct and harmonise the datasets into a hemisphere merged timeseries. Because each laboratory uses slightly different methods, we adjusted the data to make it directly comparable. This allowed us to create a consistent record of atmospheric methane concentration and its isotopes from 1988 to 2023.
Shigeyuki Ishidoya, Satoshi Sugawara, and Atsushi Okazaki
Atmos. Chem. Phys., 25, 1965–1987, https://doi.org/10.5194/acp-25-1965-2025, https://doi.org/10.5194/acp-25-1965-2025, 2025
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The 18O/16O ratio of atmospheric oxygen, δatm(18O), is higher than that of ocean water due to isotopic effects during biospheric activities. This is known as the Dole–Morita effect, and its millennial-scale variations are recorded in ice cores. However, small variations of δatm(18O) in the present day have never been detected so far. This paper presents the first observations of diurnal, seasonal, and secular variations in δatm(18O) and applies them to evaluate oxygen, carbon, and water cycles.
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Preprint archived
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Our study compares model CO2 with aircraft and OCO-2 data to identify transport model errors to better policy-related flux estimation. The model align better with aircraft data than satellite data, especially over oceans, but struggles near the surface due to inaccurate CO2 estimates. Over the Amazon and Asian megacities, differences arise from limited measurements and coarse model resolution, highlighting the need for improved monitoring and higher-resolution data to capture emissions better.
Hideki Nara, Takuya Saito, Taku Umezawa, and Yasunori Tohjima
Atmos. Meas. Tech., 17, 5187–5200, https://doi.org/10.5194/amt-17-5187-2024, https://doi.org/10.5194/amt-17-5187-2024, 2024
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We have developed a high-accuracy dynamic dilution system for generating reference gas mixtures containing carbonyl sulfide (COS). Although COS at ambient levels generally has poor storage stability, our approach involves the dilution of a gas mixture containing micromole-per-mole levels of COS, the stability of which was validated for more than 1 decade. The developed system has excellent dilution performance and will facilitate accurate instrumental calibration for atmospheric COS observation.
Shigeyuki Ishidoya, Kazuhiro Tsuboi, Hiroaki Kondo, Kentaro Ishijima, Nobuyuki Aoki, Hidekazu Matsueda, and Kazuyuki Saito
Atmos. Chem. Phys., 24, 1059–1077, https://doi.org/10.5194/acp-24-1059-2024, https://doi.org/10.5194/acp-24-1059-2024, 2024
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A method evaluating techniques for carbon neutrality, such as carbon capture and storage (CCS), is important. This study presents a method to evaluate CO2 emissions from a cement plant based on atmospheric O2 and CO2 measurements. The method will also be useful for evaluating CO2 capture from flue gas at CCS plants, since the plants remove CO2 from the atmosphere without causing any O2 changes, just as cement plants do, differing only in the direction of CO2 exchange with the atmosphere.
Kazuki Kamezaki, Sebastian O. Danielache, Shigeyuki Ishidoya, Takahisa Maeda, and Shohei Murayama
Atmos. Meas. Tech. Discuss., https://doi.org/10.5194/amt-2023-209, https://doi.org/10.5194/amt-2023-209, 2023
Revised manuscript not accepted
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Recently, MIRA Pico, a portable continuous carbonyl sulfide (COS) concentration analyzer using mid-infrared absorption, has been released. MIRA Pico has a lower cost and is smaller than conventional laser COS analyzers. However, actual COS atmospheric measurement results using MIRA Pico have not yet been reported. In this study, we modified and tested the MIRA Pico for atmospheric COS concentration measurements. We used the modified MIRA Pico for observations at Tsukuba, Japan.
Sourish Basu, Xin Lan, Edward Dlugokencky, Sylvia Michel, Stefan Schwietzke, John B. Miller, Lori Bruhwiler, Youmi Oh, Pieter P. Tans, Francesco Apadula, Luciana V. Gatti, Armin Jordan, Jaroslaw Necki, Motoki Sasakawa, Shinji Morimoto, Tatiana Di Iorio, Haeyoung Lee, Jgor Arduini, and Giovanni Manca
Atmos. Chem. Phys., 22, 15351–15377, https://doi.org/10.5194/acp-22-15351-2022, https://doi.org/10.5194/acp-22-15351-2022, 2022
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Atmospheric methane (CH4) has been growing steadily since 2007 for reasons that are not well understood. Here we determine sources of methane using a technique informed by atmospheric measurements of CH4 and its isotopologue 13CH4. Measurements of 13CH4 provide for better separation of microbial, fossil, and fire sources of methane than CH4 measurements alone. Compared to previous assessments such as the Global Carbon Project, we find a larger microbial contribution to the post-2007 increase.
Nobuyuki Aoki, Shigeyuki Ishidoya, Shohei Murayama, and Nobuhiro Matsumoto
Atmos. Meas. Tech., 15, 5969–5983, https://doi.org/10.5194/amt-15-5969-2022, https://doi.org/10.5194/amt-15-5969-2022, 2022
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The CO2 concentration in a cylinder is affected by carbon dioxide (CO2) adsorption to a cylinder’s internal surface and fractionation of CO2 and air in the preparation of standard mixtures. We demonstrate that the effects make the CO2 molar fractions deviate in standard mixtures prepared by diluting pure CO2 with air three times. This means that CO2 standard gases are difficult to gravimetrically prepare through multistep dilution.
Naveen Chandra, Prabir K. Patra, Yousuke Niwa, Akihiko Ito, Yosuke Iida, Daisuke Goto, Shinji Morimoto, Masayuki Kondo, Masayuki Takigawa, Tomohiro Hajima, and Michio Watanabe
Atmos. Chem. Phys., 22, 9215–9243, https://doi.org/10.5194/acp-22-9215-2022, https://doi.org/10.5194/acp-22-9215-2022, 2022
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This paper is intended to accomplish two goals: (1) quantify mean and uncertainty in non-fossil-fuel CO2 fluxes estimated by inverse modeling and (2) provide in-depth analyses of regional CO2 fluxes in support of emission mitigation policymaking. CO2 flux variability and trends are discussed concerning natural climate variability and human disturbances using multiple lines of evidence.
Shigeyuki Ishidoya, Kazuhiro Tsuboi, Yosuke Niwa, Hidekazu Matsueda, Shohei Murayama, Kentaro Ishijima, and Kazuyuki Saito
Atmos. Chem. Phys., 22, 6953–6970, https://doi.org/10.5194/acp-22-6953-2022, https://doi.org/10.5194/acp-22-6953-2022, 2022
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The atmospheric O2 / N2 ratio and CO2 concentration over the western North Pacific are presented. We found significant modification of the seasonal APO cycle in the middle troposphere due to the interhemispheric mixing of air. APO driven by the net marine biological activities indicated annual sea–air O2 flux during El Niño. Terrestrial biospheric and oceanic CO2 uptakes during 2012–2019 were estimated to be 1.8 and 2.8 Pg C a−1, respectively.
Taku Umezawa, Satoshi Sugawara, Kenji Kawamura, Ikumi Oyabu, Stephen J. Andrews, Takuya Saito, Shuji Aoki, and Takakiyo Nakazawa
Atmos. Chem. Phys., 22, 6899–6917, https://doi.org/10.5194/acp-22-6899-2022, https://doi.org/10.5194/acp-22-6899-2022, 2022
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Greenhouse gas methane in the Arctic atmosphere has not been accurately reported for 1900–1980 from either direct observations or ice core reconstructions. By using trace gas data from firn (compacted snow layers above ice sheet), air samples at two Greenland sites, and a firn air transport model, this study suggests a likely range of the Arctic methane reconstruction for the 20th century. Atmospheric scenarios from two previous studies are also evaluated for consistency with the firn data sets.
Ikumi Oyabu, Kenji Kawamura, Tsutomu Uchida, Shuji Fujita, Kyotaro Kitamura, Motohiro Hirabayashi, Shuji Aoki, Shinji Morimoto, Takakiyo Nakazawa, Jeffrey P. Severinghaus, and Jacob D. Morgan
The Cryosphere, 15, 5529–5555, https://doi.org/10.5194/tc-15-5529-2021, https://doi.org/10.5194/tc-15-5529-2021, 2021
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We present O2/N2 and Ar/N2 records from the Dome Fuji ice core through the bubbly ice, bubble–clathrate transition, and clathrate ice zones without gas-loss fractionation. The insolation signal is preserved through the clathrate formation. The relationship between Ar/Ν2 and Ο2/Ν2 suggests that the fractionation for the bubble–clathrate transition is mass independent, while the bubble close-off process involves a combination of mass-independent and mass-dependent fractionation for O2 and Ar.
Nobuyuki Aoki, Shigeyuki Ishidoya, Yasunori Tohjima, Shinji Morimoto, Ralph F. Keeling, Adam Cox, Shuichiro Takebayashi, and Shohei Murayama
Atmos. Meas. Tech., 14, 6181–6193, https://doi.org/10.5194/amt-14-6181-2021, https://doi.org/10.5194/amt-14-6181-2021, 2021
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Observing the minimal long-term change in atmospheric O2 molar fraction combined with CO2 observation enables us to estimate terrestrial biospheric and oceanic CO2 uptakes separately. In this study, we firstly identified the span offset between the laboratory O2 scales using our developed high-precision standard mixtures, suggesting that the result may allow us to estimate terrestrial biospheric and oceanic CO2 uptakes precisely.
Yosuke Niwa, Yousuke Sawa, Hideki Nara, Toshinobu Machida, Hidekazu Matsueda, Taku Umezawa, Akihiko Ito, Shin-Ichiro Nakaoka, Hiroshi Tanimoto, and Yasunori Tohjima
Atmos. Chem. Phys., 21, 9455–9473, https://doi.org/10.5194/acp-21-9455-2021, https://doi.org/10.5194/acp-21-9455-2021, 2021
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Fires in Equatorial Asia release a large amount of carbon into the atmosphere. Extensively using high-precision atmospheric carbon dioxide (CO2) data from a commercial aircraft observation project, we estimated fire carbon emissions in Equatorial Asia induced by the big El Niño event in 2015. Additional shipboard measurement data elucidated the validity of the analysis and the best estimate indicated 273 Tg C for fire emissions during September–October 2015.
Shigeyuki Ishidoya, Satoshi Sugawara, Yasunori Tohjima, Daisuke Goto, Kentaro Ishijima, Yosuke Niwa, Nobuyuki Aoki, and Shohei Murayama
Atmos. Chem. Phys., 21, 1357–1373, https://doi.org/10.5194/acp-21-1357-2021, https://doi.org/10.5194/acp-21-1357-2021, 2021
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The surface Ar / N2 ratio showed not only secular increasing trends, but also interannual variations in phase with the global ocean heat content (OHC). Sensitivity test by using a two-dimensional model indicated that the secular trend in the Ar / N2 ratio is modified by the gravitational separation in the stratosphere. The analytical results imply that the surface Ar/N2 ratio is an important tracer for detecting spatiotemporally integrated changes in OHC and stratospheric circulation.
Ikumi Oyabu, Kenji Kawamura, Kyotaro Kitamura, Remi Dallmayr, Akihiro Kitamura, Chikako Sawada, Jeffrey P. Severinghaus, Ross Beaudette, Anaïs Orsi, Satoshi Sugawara, Shigeyuki Ishidoya, Dorthe Dahl-Jensen, Kumiko Goto-Azuma, Shuji Aoki, and Takakiyo Nakazawa
Atmos. Meas. Tech., 13, 6703–6731, https://doi.org/10.5194/amt-13-6703-2020, https://doi.org/10.5194/amt-13-6703-2020, 2020
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Air in polar ice cores provides information on past atmosphere and climate. We present a new method for simultaneously measuring eight gases (CH4, N2O and CO2 concentrations; isotopic ratios of N2 and O2; elemental ratios between N2, O2 and Ar; and total air content) from single ice-core samples with high precision.
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Short summary
We have collected stratospheric air samples using balloon-borne cryogenic samplers over Japan since 1985 and analyzed them for δ13CO2. δ13CO2 has decreased through time in the mid-stratosphere with an average rate of change of −0.026 ± 0.001 ‰ yr−1. We found that stratospheric δ13CO2 variations are governed by airborne production of 13C-depleted CO2 by CH4 oxidation, gravitational separation, and propagation of the decreasing tropospheric δ13CO2 trend into the stratosphere.
We have collected stratospheric air samples using balloon-borne cryogenic samplers over Japan...
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