Research article 16 Mar 2017
Research article | 16 Mar 2017
Seasonal variations of triple oxygen isotopic compositions of atmospheric sulfate, nitrate, and ozone at Dumont d'Urville, coastal Antarctica
Sakiko Ishino et al.
Related authors
Kun Wang, Shohei Hattori, Mang Lin, Sakiko Ishino, Becky Alexander, Kazuki Kamezaki, Naohiro Yoshida, and Shichang Kang
Atmos. Chem. Phys. Discuss., https://doi.org/10.5194/acp-2020-1279, https://doi.org/10.5194/acp-2020-1279, 2021
Preprint under review for ACP
Short summary
Short summary
Sulfate aerosols play an important climatic role and exert adverse effects on the ecological environment and human health. In this study, we present the triple oxygen isotopic composition of sulfate from the Mt. Everest region, southern Tibetan Plateau, and deciphered the formation mechanisms of atmospheric sulfate in this pristine environment. The results indicate the important role of the S(IV) + O3 pathway in atmospheric sulfate formation promoted by high cloud water pH conditions.
Kun Wang, Shohei Hattori, Mang Lin, Sakiko Ishino, Becky Alexander, Kazuki Kamezaki, Naohiro Yoshida, and Shichang Kang
Atmos. Chem. Phys. Discuss., https://doi.org/10.5194/acp-2020-1279, https://doi.org/10.5194/acp-2020-1279, 2021
Preprint under review for ACP
Short summary
Short summary
Sulfate aerosols play an important climatic role and exert adverse effects on the ecological environment and human health. In this study, we present the triple oxygen isotopic composition of sulfate from the Mt. Everest region, southern Tibetan Plateau, and deciphered the formation mechanisms of atmospheric sulfate in this pristine environment. The results indicate the important role of the S(IV) + O3 pathway in atmospheric sulfate formation promoted by high cloud water pH conditions.
Sarah Albertin, Joël Savarino, Slimane Bekki, Albane Barbero, and Nicolas Caillon
Atmos. Chem. Phys. Discuss., https://doi.org/10.5194/acp-2020-1143, https://doi.org/10.5194/acp-2020-1143, 2020
Preprint under review for ACP
Short summary
Short summary
We report an efficient method to collect atmospheric NO2 adapted for isotopic analysis and present the first measurements of NO2 triple oxygen isotopes and double nitrogen isotopes. Atmospheric samplings carried out in Grenoble, France, highlight the sensitivity of NO2 isotopic signatures to the local NOx emissions and chemical regimes. The quantification of the NO2 oxygen isotope anomaly opens new perspectives in the study of the NOx oxidation pathways to nitrate.
Christian Vincent, Diego Cusicanqui, Bruno Jourdain, Olivier Laarman, Delphine Six, Adrien Gilbert, Andrea Walpersdorf, Antoine Rabatel, Luc Piard, Florent Gimbert, Olivier Gagliardini, Vincent Peyaud, Laurent Arnaud, Emmanuel Thibert, Fanny Brun, and Ugo Nanni
The Cryosphere Discuss., https://doi.org/10.5194/tc-2020-239, https://doi.org/10.5194/tc-2020-239, 2020
Revised manuscript accepted for TC
Short summary
Short summary
In situ glacier point mass-balances data are crucial to assess climate change in different regions of the world. Unfortunately, these data are rare because huge efforts are required to conduct in situ measurements on glaciers. Here, we propose a new approach from remote sensing observations. The method has been tested on Argentière and Mer de Glace glaciers (France). It should be possible to apply this method to high spatial resolution satellite images as well on numerous glaciers in the world.
Albane Barbero, Camille Blouzon, Joël Savarino, Nicolas Caillon, Aurélien Dommergue, and Roberto Grilli
Atmos. Meas. Tech., 13, 4317–4331, https://doi.org/10.5194/amt-13-4317-2020, https://doi.org/10.5194/amt-13-4317-2020, 2020
Short summary
Short summary
In this paper, we present a compact, affordable and robust instrument for in situ measurements of different trace gases: NOx, IO, CHOCHO and O3 with very low detection limits. The device weighs 15 kg and has a total electrical power consumption of < 300 W. Its very low detection limits and its design make it suitable for field applications to address different questions such as how to better constrain the oxidative capacity of the atmosphere and study the chemistry of highly reactive species.
V. Holly L. Winton, Alison Ming, Nicolas Caillon, Lisa Hauge, Anna E. Jones, Joel Savarino, Xin Yang, and Markus M. Frey
Atmos. Chem. Phys., 20, 5861–5885, https://doi.org/10.5194/acp-20-5861-2020, https://doi.org/10.5194/acp-20-5861-2020, 2020
Short summary
Short summary
The transfer of the nitrogen stable isotopic composition in nitrate between the air and snow at low accumulation sites in Antarctica leaves an UV imprint in the snow. Quantifying how nitrate isotope values change allows us to interpret longer ice core records. Based on nitrate observations and modelling at Kohnen, East Antarctica, the dominant factors controlling the nitrate isotope signature in deep snow layers are the depth of light penetration into the snowpack and the snow accumulation rate.
Tamaki Fujinawa, Tomohiro O. Sato, Takayoshi Yamada, Seidai Nara, Yuki Uchiyama, Kodai Takahashi, Naohiro Yoshida, and Yasuko Kasai
Atmos. Meas. Tech., 13, 2119–2129, https://doi.org/10.5194/amt-13-2119-2020, https://doi.org/10.5194/amt-13-2119-2020, 2020
Short summary
Short summary
We performed an error analysis of SMILES observations for acetonitrile and a validation using the MLS observations by extracting the coincident points between SMILES and MLS data. The major error sources for the SMILES observations were quantitatively estimated. At upper pressure levels the difference between the two datasets increased because of an uncertainty in MLS observations. The results showed that SMILES has an advantage in measuring acetonitrile in the upper stratosphere and mesosphere.
Christian Vincent, Adrien Gilbert, Bruno Jourdain, Luc Piard, Patrick Ginot, Vladimir Mikhalenko, Philippe Possenti, Emmanuel Le Meur, Olivier Laarman, and Delphine Six
The Cryosphere, 14, 925–934, https://doi.org/10.5194/tc-14-925-2020, https://doi.org/10.5194/tc-14-925-2020, 2020
Short summary
Short summary
We observed very low glacier thickness changes over the last decades at very-high-elevation glaciated areas on Mont Blanc. Conversely, measurements performed in deep boreholes since 1994 reveal strong changes in englacial temperature reaching 1.5 °C at a depth of 50 m. We conclude that at such very high elevations, current changes in climate do not lead to visible changes in glacier thickness but cause invisible changes within the glacier in terms of englacial temperatures.
Detlev Helmig, Daniel Liptzin, Jacques Hueber, and Joel Savarino
The Cryosphere, 14, 199–209, https://doi.org/10.5194/tc-14-199-2020, https://doi.org/10.5194/tc-14-199-2020, 2020
Short summary
Short summary
We present 15 months of trace gas observations from air withdrawn within the snowpack and from above the snow at Concordia Station in Antarctica. The data show occasional positive spikes, indicative of pollution from the station generator. The pollution signal can be seen in snowpack air shortly after it is observed above the snow surface, and lasting for up to several days, much longer than above the surface.
Stanislav Kutuzov, Michel Legrand, Susanne Preunkert, Patrick Ginot, Vladimir Mikhalenko, Karim Shukurov, Aleksei Poliukhov, and Pavel Toropov
Atmos. Chem. Phys., 19, 14133–14148, https://doi.org/10.5194/acp-19-14133-2019, https://doi.org/10.5194/acp-19-14133-2019, 2019
Short summary
Short summary
Ice cores are one of the most valuable paleo-archives. Here we present analysis of the concentrations of calcium, recorded in ice core from the Caucasus over the past 240 years. We found a correlation between dust in ice and precipitation and soil moisture content in the Middle East and North Africa. The prominent increase in dust concentration in the ice core confirms that the recent droughts in the Fertile Crescent were most severe at least for the past two centuries.
Susanne Preunkert, Michel Legrand, Stanislav Kutuzov, Patrick Ginot, Vladimir Mikhalenko, and Ronny Friedrich
Atmos. Chem. Phys., 19, 14119–14132, https://doi.org/10.5194/acp-19-14119-2019, https://doi.org/10.5194/acp-19-14119-2019, 2019
Short summary
Short summary
This paper reports on an ice core drilled to bedrock at Mt Elbrus (5115 m a.s.l., Russia) to reconstruct the atmospheric pollution since the 19th century in south-eastern Europe. The annual dust-free sulfate record indicates a 7-fold increase from prior to 1900 to 1980–1995. Consistent with past SO2 emission inventories, a much earlier onset and a more pronounced decrease in the sulfur pollution over the last 3 decades are observed in western Europe than in south-eastern and eastern Europe.
Sentia Goursaud, Valérie Masson-Delmotte, Vincent Favier, Suzanne Preunkert, Michel Legrand, Bénédicte Minster, and Martin Werner
The Cryosphere, 13, 1297–1324, https://doi.org/10.5194/tc-13-1297-2019, https://doi.org/10.5194/tc-13-1297-2019, 2019
Short summary
Short summary
We report new water stable isotope records from the first highly resolved firn core drilled in Adélie Land and covering 1998–2014. Using an updated database, we show that mean values are in line with the range of coastal values. Statistical analyses show no relationship between our record and local surface air temperature. Atmospheric back trajectories and isotopic simulations suggest that water stable isotopes in Adélie provide a fingerprint of the variability of atmospheric dynamics.
Kazuki Kamezaki, Shohei Hattori, Enno Bahlmann, and Naohiro Yoshida
Atmos. Meas. Tech., 12, 1141–1154, https://doi.org/10.5194/amt-12-1141-2019, https://doi.org/10.5194/amt-12-1141-2019, 2019
Short summary
Short summary
Knowledge related to sulfur isotopic composition of carbonyl sulfide (OCS or COS), the most abundant atmospheric sulfur species, remains scarce. We present a new sampling system for collecting approx. 10 nmol of OCS from ambient air coupled with a purification system. The system presented herein is useful for application of sulfur isotopic compositions for investigation of OCS sources and sinks in the troposphere to elucidate its cycle and its contribution to background stratospheric sulfate.
Tommaso Galeazzo, Slimane Bekki, Erwan Martin, Joël Savarino, and Stephen R. Arnold
Atmos. Chem. Phys., 18, 17909–17931, https://doi.org/10.5194/acp-18-17909-2018, https://doi.org/10.5194/acp-18-17909-2018, 2018
Short summary
Short summary
Volcanic sulfur can have climatic impacts for the planet via sulfate aerosol formation, leading also to pollution events. We provide model constraints on tropospheric volcanic sulfate formation, with implications for its lifetime and impacts on regional air quality. Oxygen isotope investigations from our model suggest that in the poor tropospheric plumes of halogens, the O2/TMI sulfur oxidation pathway might significantly control sulfate production. The produced sulfate has no isotopic anomaly.
Shaojie Song, Hélène Angot, Noelle E. Selin, Hubert Gallée, Francesca Sprovieri, Nicola Pirrone, Detlev Helmig, Joël Savarino, Olivier Magand, and Aurélien Dommergue
Atmos. Chem. Phys., 18, 15825–15840, https://doi.org/10.5194/acp-18-15825-2018, https://doi.org/10.5194/acp-18-15825-2018, 2018
Short summary
Short summary
Mercury is a trace metal with adverse health effects on human and wildlife. Its unique property makes it undergo long-range transport, and even remote Antarctica receives significant inputs. This paper presents the first model that aims to understand mercury behavior over the Antarctic Plateau. We find that mercury is quickly cycled between snow and air in the sunlit period, likely driven by bromine chemistry, and that several uncertain processes contribute to its behavior in the dark period.
Rolf Weller, Michel Legrand, and Susanne Preunkert
Atmos. Chem. Phys., 18, 2413–2430, https://doi.org/10.5194/acp-18-2413-2018, https://doi.org/10.5194/acp-18-2413-2018, 2018
Short summary
Short summary
We measured aerosol size distributions and the composition of summer aerosol at the continental Antarctic station Kohnen. Two different weather conditions mediated the transport of aerosol: (1) the intermittent impact of cyclones associated with outstanding marine aerosol concentrations and new particle formation and (2) steady long-range transport under prevailing clear sky conditions. The latter air masses were characterized by aged aerosol and less aerosol load.
Sakae Toyoda, Naohiro Yoshida, Shinji Morimoto, Shuji Aoki, Takakiyo Nakazawa, Satoshi Sugawara, Shigeyuki Ishidoya, Mitsuo Uematsu, Yoichi Inai, Fumio Hasebe, Chusaku Ikeda, Hideyuki Honda, and Kentaro Ishijima
Atmos. Chem. Phys., 18, 833–844, https://doi.org/10.5194/acp-18-833-2018, https://doi.org/10.5194/acp-18-833-2018, 2018
Short summary
Short summary
By analysis of whole air samples collected by balloon-borne compact cryogenic samplers, we found that apparent isotope effect for stratospheric N2O between 25 and 30 km over the Equator is larger than that observed in other latitudes and that it is almost equal to the effect predicted by laboratory simulation experiments. These results suggest that equatorial middle stratosphere can be treated as an isolated region when we consider the decomposition of N2O by photochemical processes.
Michel Legrand, Susanne Preunkert, Rolf Weller, Lars Zipf, Christoph Elsässer, Silke Merchel, Georg Rugel, and Dietmar Wagenbach
Atmos. Chem. Phys., 17, 14055–14073, https://doi.org/10.5194/acp-17-14055-2017, https://doi.org/10.5194/acp-17-14055-2017, 2017
Short summary
Short summary
Levels of MSA and sulfate at inland Antarctica are documented from multiple year-round records of bulk and size-segregated aerosol samplings. A striking difference in the seasonality of sulfur aerosol composition, characterized by a MSA to nssSO4 ratio reaching a minimum in summer over the Antarctic plateau (0.05) and a maximum at the coast (up to 0.40), is clearly established. An efficient chemical destruction of MSA is suggested to take place over the Antarctic plateau in summer.
Michel Legrand, Susanne Preunkert, Eric Wolff, Rolf Weller, Bruno Jourdain, and Dietmar Wagenbach
Atmos. Chem. Phys., 17, 14039–14054, https://doi.org/10.5194/acp-17-14039-2017, https://doi.org/10.5194/acp-17-14039-2017, 2017
Short summary
Short summary
Multiple year-round records of bulk and size-segregated composition of sea-salt aerosol and acidic gases (HCl and HNO3) were obtained at inland Antarctica. Both acidic sulfur particles and nitric acid are involved in the observed sea-salt dechlorination in spring/summer. The observed sulfate to sodium mass ratio of sea-salt aerosol in winter (0.16 ± 0.05) suggests on average a similar contribution of sea-ice and open-ocean emissions to the sea-salt load over inland Antarctica at that season.
Anna Kozachek, Vladimir Mikhalenko, Valérie Masson-Delmotte, Alexey Ekaykin, Patrick Ginot, Stanislav Kutuzov, Michel Legrand, Vladimir Lipenkov, and Susanne Preunkert
Clim. Past, 13, 473–489, https://doi.org/10.5194/cp-13-473-2017, https://doi.org/10.5194/cp-13-473-2017, 2017
Sentia Goursaud, Valérie Masson-Delmotte, Vincent Favier, Susanne Preunkert, Michel Fily, Hubert Gallée, Bruno Jourdain, Michel Legrand, Olivier Magand, Bénédicte Minster, and Martin Werner
The Cryosphere, 11, 343–362, https://doi.org/10.5194/tc-11-343-2017, https://doi.org/10.5194/tc-11-343-2017, 2017
Short summary
Short summary
Uncertainty of sea level changes is a challenge. As Antarctica is the biggest water reservoir, it is necessary to know how it will contribute. To be able to simulate it, an understanding of past climate is to be achieved, for instance, by studying the ice cores. As climate change is different in different regions, observations are needed all over the continent. Studying an ice core in Adélie Land, we can conclude that there are no changes there at decadal scale over the period 1947–2007.
Michel Legrand, Joseph McConnell, Hubertus Fischer, Eric W. Wolff, Susanne Preunkert, Monica Arienzo, Nathan Chellman, Daiana Leuenberger, Olivia Maselli, Philip Place, Michael Sigl, Simon Schüpbach, and Mike Flannigan
Clim. Past, 12, 2033–2059, https://doi.org/10.5194/cp-12-2033-2016, https://doi.org/10.5194/cp-12-2033-2016, 2016
Short summary
Short summary
Here, we review previous attempts made to reconstruct past forest fire using chemical signals recorded in Greenland ice. We showed that the Greenland ice records of ammonium, found to be a good fire proxy, consistently indicate changing fire activity in Canada in response to past climatic conditions that occurred since the last 15 000 years, including the Little Ice Age and the last large climatic transition.
Josué Bock, Joël Savarino, and Ghislain Picard
Atmos. Chem. Phys., 16, 12531–12550, https://doi.org/10.5194/acp-16-12531-2016, https://doi.org/10.5194/acp-16-12531-2016, 2016
Short summary
Short summary
We develop a physically based parameterisation of the co-condensation process. Our model includes solid-state diffusion within a snow grain. It reproduces with good agreement the nitrate measurement in surface snow. Winter and summer concentrations are driven respectively by thermodynamic equilibrium and co-condensation. Adsorbed nitrate likely accounts for a minor part. This work shows that co-condensation is required to explain the chemical composition of snow undergoing temperature gradient.
Hélène Angot, Iris Dion, Nicolas Vogel, Michel Legrand, Olivier Magand, and Aurélien Dommergue
Atmos. Chem. Phys., 16, 8265–8279, https://doi.org/10.5194/acp-16-8265-2016, https://doi.org/10.5194/acp-16-8265-2016, 2016
Short summary
Short summary
This paper presents a multi-year record of atmospheric gaseous elemental mercury (Hg(0)) at Dumont d’Urville (DDU) on the East Antarctic coast. This record reveals particularities that are not seen at other coastal Antarctic sites, likely due to the more frequent arrival of inland air masses at DDU than at other coastal sites, and to the influence of oceanic air masses. This study confirms the influence of processes observed inland on the cycle of atmospheric mercury at a continental scale.
Michel Legrand, Susanne Preunkert, Joël Savarino, Markus M. Frey, Alexandre Kukui, Detlev Helmig, Bruno Jourdain, Anna E. Jones, Rolf Weller, Neil Brough, and Hubert Gallée
Atmos. Chem. Phys., 16, 8053–8069, https://doi.org/10.5194/acp-16-8053-2016, https://doi.org/10.5194/acp-16-8053-2016, 2016
Short summary
Short summary
Surface ozone, the most abundant atmospheric oxidant, has been measured since 2004 at the coastal East Antarctic site of Dumont d’Urville, and since 2007 at the Concordia station located on the high East Antarctic plateau. Long-term changes, seasonal and diurnal cycles, as well as inter-annual summer variability observed at these two East Antarctic sites are discussed. Influences like sea ice extent and outflow from inland Antarctica are discussed.
Sakae Toyoda and Naohiro Yoshida
Atmos. Meas. Tech., 9, 2093–2101, https://doi.org/10.5194/amt-9-2093-2016, https://doi.org/10.5194/amt-9-2093-2016, 2016
Short summary
Short summary
Tiny variation in natural abundance ratios of stable isotopes of nitrogen and oxygen in nitrous oxide (N2O) can be used as a fingerprint of this trace gas that causes greenhouse effect and stratospheric ozone depletion. Toward the understanding of the global budget of N2O and its temporal change, we developed an automated sample preparation system that can be used to measure the stable isotope ratios in N2O in various air samples collected into flasks with high precision and less labor.
Alexandra Touzeau, Amaëlle Landais, Barbara Stenni, Ryu Uemura, Kotaro Fukui, Shuji Fujita, Sarah Guilbaud, Alexey Ekaykin, Mathieu Casado, Eugeni Barkan, Boaz Luz, Olivier Magand, Grégory Teste, Emmanuel Le Meur, Mélanie Baroni, Joël Savarino, Ilann Bourgeois, and Camille Risi
The Cryosphere, 10, 837–852, https://doi.org/10.5194/tc-10-837-2016, https://doi.org/10.5194/tc-10-837-2016, 2016
Short summary
Short summary
The relationship between water isotope ratios and temperature is investigated in precipitation snow at Vostok and Dome C, as well as in surface snow along traverses. The temporal slope of the linear regression for the precipitation is smaller than the geographical slope. Thus, using the latter could lead to an underestimation of past temperature changes. The processes active at remote sites (best glacial analogs) are explored through a combination of water isotopes in short snow pits.
Joël Savarino, William C. Vicars, Michel Legrand, Suzanne Preunkert, Bruno Jourdain, Markus M. Frey, Alexandre Kukui, Nicolas Caillon, and Jaime Gil Roca
Atmos. Chem. Phys., 16, 2659–2673, https://doi.org/10.5194/acp-16-2659-2016, https://doi.org/10.5194/acp-16-2659-2016, 2016
Short summary
Short summary
Atmospheric nitrate is collected on the East Antarctic ice sheet. Nitrogen and oxygen stable isotopes and concentrations of nitrate are measured. Using a box model, we show that there is s systematic discrepancy between observations and model results. We suggest that this discrepancy probably results from unknown NOx chemistry above the Antarctic ice sheet. However, possible misconception in the stable isotope mass balance is not completely excluded.
Koki Maeda, Sakae Toyoda, Midori Yano, Shohei Hattori, Makoto Fukasawa, Keiichi Nakajima, and Naohiro Yoshida
Biogeosciences, 13, 1341–1349, https://doi.org/10.5194/bg-13-1341-2016, https://doi.org/10.5194/bg-13-1341-2016, 2016
Short summary
Short summary
Nitrogen isotope ratios (δ15N) of NH4+ in dairy manure compost piles were studied. The δ15N–NH4+ values in different pile zones (top, side and core) show that extremely high nitrogen conversion, nitrification–denitrification activity of the microbes and NH3 volatilization occurred in pile top zone, which has very high NH4+ concentrations and significantly high 15N (δ15N: 12.7–29.8 ‰) values.
N. Zannoni, V. Gros, M. Lanza, R. Sarda, B. Bonsang, C. Kalogridis, S. Preunkert, M. Legrand, C. Jambert, C. Boissard, and J. Lathiere
Atmos. Chem. Phys., 16, 1619–1636, https://doi.org/10.5194/acp-16-1619-2016, https://doi.org/10.5194/acp-16-1619-2016, 2016
Short summary
Short summary
Our manuscript shows results of OH reactivity and Biogenic Volatile Organic Compounds (BVOCs) concentration during a field experiment conducted in late spring 2014 at the Observatoire de Haute Provence (OHP) site. We found that OH reactivity is among the highest measured in forests globally (69 s−1) and it is mainly due to isoprene. No missing reactivity was present during daytime inside or above the canopy, while 50 % missing reactivity was found by night at both heights.
E. Gautier, J. Savarino, J. Erbland, A. Lanciki, and P. Possenti
Clim. Past, 12, 103–113, https://doi.org/10.5194/cp-12-103-2016, https://doi.org/10.5194/cp-12-103-2016, 2016
Short summary
Short summary
We evaluate the local-scale variability of a sulfate profile at a low-accumulation site (Dome C, Antarctica) to assess the representativeness of one ice core for volcanic reconstructions. Peak statistical occurrence, depth and flux variability are evaluated from five cores. Due to local-scale variability, 64 volcanic peaks can be identified by a five-cores analysis, while only half of them can be assessed from two cores. Using five cores, the uncertainty of the mean flux is reduced to 29 %.
V. Mikhalenko, S. Sokratov, S. Kutuzov, P. Ginot, M. Legrand, S. Preunkert, I. Lavrentiev, A. Kozachek, A. Ekaykin, X. Faïn, S. Lim, U. Schotterer, V. Lipenkov, and P. Toropov
The Cryosphere, 9, 2253–2270, https://doi.org/10.5194/tc-9-2253-2015, https://doi.org/10.5194/tc-9-2253-2015, 2015
Short summary
Short summary
For the first time an ice core unaffected by melting was recovered from the western Elbrus plateau in the Caucasus. The preserved chemical and isotopic data are considered a source of paleo-climate information for southern/eastern Europe. Considerable snow accumulation (about 1500mm w.e.) and high sampling resolution allowed seasonal variability to be obtained in climate signals, covering a time period of about 200 years. Ice flow models suggest that the basal ice age can be more than 600 years.
J. Erbland, J. Savarino, S. Morin, J. L. France, M. M. Frey, and M. D. King
Atmos. Chem. Phys., 15, 12079–12113, https://doi.org/10.5194/acp-15-12079-2015, https://doi.org/10.5194/acp-15-12079-2015, 2015
Short summary
Short summary
In this paper, we describe the development of a numerical model which aims at representing nitrate recycling at the air-snow interface on the East Antarctic Plateau. Stable isotopes are used as diagnostic and evaluation tools by comparing the model's results to recent field measurements of nitrate and key atmospheric species at Dome C, Antarctica. From sensitivity tests conducted with the model, we propose a framework for the interpretation of the nitrate isotope record in deep ice cores.
T. A. Berhanu, J. Savarino, J. Erbland, W. C. Vicars, S. Preunkert, J. F. Martins, and M. S. Johnson
Atmos. Chem. Phys., 15, 11243–11256, https://doi.org/10.5194/acp-15-11243-2015, https://doi.org/10.5194/acp-15-11243-2015, 2015
Short summary
Short summary
In this field study at Dome C, Antarctica, we investigated the effect of solar UV photolysis on the stable isotopes of nitrate in snow via comparison of two identical snow pits while exposing only one to solar UV. From the difference between the average isotopic fractionations calculated for each pit, we determined a purely photolytic nitrogen isotopic fractionation of -55.8‰, in good agreement with what has been recently determined in a laboratory study.
K. Ishijima, M. Takigawa, K. Sudo, S. Toyoda, N. Yoshida, T. Röckmann, J. Kaiser, S. Aoki, S. Morimoto, S. Sugawara, and T. Nakazawa
Atmos. Chem. Phys. Discuss., https://doi.org/10.5194/acpd-15-19947-2015, https://doi.org/10.5194/acpd-15-19947-2015, 2015
Revised manuscript not accepted
Short summary
Short summary
We developed an atmospheric N2O isotopocule model based on a chemistry-coupled atmospheric general circulation model and a simple method to optimize the model, and estimated the isotopic signatures of surface sources at the hemispheric scale. Data obtained from ground-based observations, measurements of firn air, and balloon and aircraft flights were used to optimize the long-term trends, interhemispheric gradients, and photolytic fractionation, respectively, in the model.
M. M. Frey, H. K. Roscoe, A. Kukui, J. Savarino, J. L. France, M. D. King, M. Legrand, and S. Preunkert
Atmos. Chem. Phys., 15, 7859–7875, https://doi.org/10.5194/acp-15-7859-2015, https://doi.org/10.5194/acp-15-7859-2015, 2015
Short summary
Short summary
Surprisingly large concentrations and flux of atmospheric nitrogen oxides were measured at Dome C, East Antarctica. It was found that the surface snow holds a significant reservoir of photochemically produced NOx and is a sink of gas-phase ozone. Main drivers of NOx snow emissions were large snow nitrate concentrations, with contributions of increased UV from decreases in stratospheric ozone. Observed halogen and hydroxyl radical concentrations were too low to explain large NO2:NO ratios.
S. Preunkert, M. Legrand, M. M. Frey, A. Kukui, J. Savarino, H. Gallée, M. King, B. Jourdain, W. Vicars, and D. Helmig
Atmos. Chem. Phys., 15, 6689–6705, https://doi.org/10.5194/acp-15-6689-2015, https://doi.org/10.5194/acp-15-6689-2015, 2015
Short summary
Short summary
During two austral summers HCHO was investigated in air, snow, and interstitial air at the Concordia site located on the East Antarctic Plateau. Snow emission fluxes were estimated to be around 1 to 2 and 3 to 5 x 10^12 molecules m-2 s-1 at night and at noon, respectively. Shading experiments suggest that the photochemical HCHO production in the snowpack at Concordia remains negligible. The mean HCHO level of 130pptv observed at 1m above the surface is quite well reproduced by 1-D simulations.
H. Gallée, S. Preunkert, S. Argentini, M. M. Frey, C. Genthon, B. Jourdain, I. Pietroni, G. Casasanta, H. Barral, E. Vignon, C. Amory, and M. Legrand
Atmos. Chem. Phys., 15, 6225–6236, https://doi.org/10.5194/acp-15-6225-2015, https://doi.org/10.5194/acp-15-6225-2015, 2015
Short summary
Short summary
Regional climate model MAR was run for the region of Dome C located on the East Antarctic plateau, during summer 2011–2012, with a high vertical resolution in the lower troposphere. MAR is generally in very good agreement with the observations and provides sufficiently reliable information about surface turbulent fluxes and vertical profiles of vertical diffusion coefficients when discussing the representativeness of chemical measurements made nearby the ground surface at Dome C.
L. Geng, J. Cole-Dai, B. Alexander, J. Erbland, J. Savarino, A. J. Schauer, E. J. Steig, P. Lin, Q. Fu, and M. C. Zatko
Atmos. Chem. Phys., 14, 13361–13376, https://doi.org/10.5194/acp-14-13361-2014, https://doi.org/10.5194/acp-14-13361-2014, 2014
Short summary
Short summary
Examinations on snowpit and firn core results from Summit, Greenland suggest that there are two mechanisms leading to the observed double nitrate peaks in some years in the industrial era: 1) long-rang transport of nitrate and 2) enhanced local photochemical production of nitrate. Both of these mechanisms are related to pollution transport, as the additional nitrate from either direct transport or enhanced local photochemistry requires enhanced nitrogen sources from anthropogenic emissions.
A. Kukui, M. Legrand, S. Preunkert, M. M. Frey, R. Loisil, J. Gil Roca, B. Jourdain, M. D. King, J. L. France, and G. Ancellet
Atmos. Chem. Phys., 14, 12373–12392, https://doi.org/10.5194/acp-14-12373-2014, https://doi.org/10.5194/acp-14-12373-2014, 2014
Short summary
Short summary
Concentrations of OH radicals and the sum of peroxy radicals, RO2, were measured in the boundary layer for the first time on the East Antarctic Plateau at the Concordia Station during the austral summer 2011/2012. The concentrations of radicals were comparable to those observed at the South Pole, confirming that the elevated oxidative capacity of the Antarctic atmospheric boundary layer found at the South Pole is not restricted to the South Pole but common over the high Antarctic plateau.
N. Zhang, K. Yamada, N. Suzuki, and N. Yoshida
Biogeosciences, 11, 5335–5348, https://doi.org/10.5194/bg-11-5335-2014, https://doi.org/10.5194/bg-11-5335-2014, 2014
M. Legrand, S. Preunkert, M. Frey, Th. Bartels-Rausch, A. Kukui, M. D. King, J. Savarino, M. Kerbrat, and B. Jourdain
Atmos. Chem. Phys., 14, 9963–9976, https://doi.org/10.5194/acp-14-9963-2014, https://doi.org/10.5194/acp-14-9963-2014, 2014
J.-C. Gallet, F. Domine, J. Savarino, M. Dumont, and E. Brun
The Cryosphere, 8, 1205–1215, https://doi.org/10.5194/tc-8-1205-2014, https://doi.org/10.5194/tc-8-1205-2014, 2014
X. Faïn, J. Chappellaz, R. H. Rhodes, C. Stowasser, T. Blunier, J. R. McConnell, E. J. Brook, S. Preunkert, M. Legrand, T. Debois, and D. Romanini
Clim. Past, 10, 987–1000, https://doi.org/10.5194/cp-10-987-2014, https://doi.org/10.5194/cp-10-987-2014, 2014
T. Yamazaki, T. Hozuki, K. Arai, S. Toyoda, K. Koba, T. Fujiwara, and N. Yoshida
Biogeosciences, 11, 2679–2689, https://doi.org/10.5194/bg-11-2679-2014, https://doi.org/10.5194/bg-11-2679-2014, 2014
T. O. Sato, H. Sagawa, N. Yoshida, and Y. Kasai
Atmos. Meas. Tech., 7, 941–958, https://doi.org/10.5194/amt-7-941-2014, https://doi.org/10.5194/amt-7-941-2014, 2014
M. Legrand, S. Preunkert, B. Jourdain, J. Guilhermet, X. Fa{ï}n, I. Alekhina, and J. R. Petit
Clim. Past, 9, 2195–2211, https://doi.org/10.5194/cp-9-2195-2013, https://doi.org/10.5194/cp-9-2195-2013, 2013
S. Preunkert and M. Legrand
Clim. Past, 9, 1403–1416, https://doi.org/10.5194/cp-9-1403-2013, https://doi.org/10.5194/cp-9-1403-2013, 2013
J. A. Schmidt, M. S. Johnson, S. Hattori, N. Yoshida, S. Nanbu, and R. Schinke
Atmos. Chem. Phys., 13, 1511–1520, https://doi.org/10.5194/acp-13-1511-2013, https://doi.org/10.5194/acp-13-1511-2013, 2013
Related subject area
Subject: Isotopes | Research Activity: Field Measurements | Altitude Range: Troposphere | Science Focus: Chemistry (chemical composition and reactions)
Baffin Bay sea ice extent and synoptic moisture transport drive water vapor isotope (δ18O, δ2H, and deuterium excess) variability in coastal northwest Greenland
New evidence for atmospheric mercury transformations in the marine boundary layer from stable mercury isotopes
The isotopic composition of atmospheric nitrous oxide observed at the high-altitude research station Jungfraujoch, Switzerland
Deposition, recycling, and archival of nitrate stable isotopes between the air–snow interface: comparison between Dronning Maud Land and Dome C, Antarctica
Oxygen and sulfur mass-independent isotopic signatures in black crusts: the complementary negative Δ33S reservoir of sulfate aerosols?
Atmospheric radiocarbon measurements to quantify CO2 emissions in the UK from 2014 to 2015
An improved estimate for the δ13C and δ18O signatures of carbon monoxide produced from atmospheric oxidation of volatile organic compounds
Seasonality in the Δ33S measured in urban aerosols highlights an additional oxidation pathway for atmospheric SO2
The Δ17O and δ18O values of atmospheric nitrates simultaneously collected downwind of anthropogenic sources – implications for polluted air masses
A very limited role of tropospheric chlorine as a sink of the greenhouse gas methane
Detection and variability of combustion-derived vapor in an urban basin
Stable sulfur isotope measurements to trace the fate of SO2 in the Athabasca oil sands region
Triple oxygen isotopes indicate urbanization affects sources of nitrate in wet and dry atmospheric deposition
Isotopic constraints on heterogeneous sulfate production in Beijing haze
Estimation of the fossil fuel component in atmospheric CO2 based on radiocarbon measurements at the Beromünster tall tower, Switzerland
Constraining N2O emissions since 1940 using firn air isotope measurements in both hemispheres
Carbon isotopic signature of coal-derived methane emissions to the atmosphere: from coalification to alteration
Isotopic composition for source identification of mercury in atmospheric fine particles
Isotopic constraints on the role of hypohalous acids in sulfate aerosol formation in the remote marine boundary layer
In situ observations of the isotopic composition of methane at the Cabauw tall tower site
Oxygen isotope mass balance of atmospheric nitrate at Dome C, East Antarctica, during the OPALE campaign
Isotopic effects of nitrate photochemistry in snow: a field study at Dome C, Antarctica
Stable carbon isotope ratios of ambient secondary organic aerosols in Toronto
WAIS Divide ice core suggests sustained changes in the atmospheric formation pathways of sulfate and nitrate since the 19th century in the extratropical Southern Hemisphere
Stable carbon isotope ratios of toluene in the boundary layer and the lower free troposphere
Emission ratio and isotopic signatures of molecular hydrogen emissions from tropical biomass burning
Can the carbon isotopic composition of methane be reconstructed from multi-site firn air measurements?
Air–snow transfer of nitrate on the East Antarctic Plateau – Part 1: Isotopic evidence for a photolytically driven dynamic equilibrium in summer
Chemical characterization and stable carbon isotopic composition of particulate Polycyclic Aromatic Hydrocarbons issued from combustion of 10 Mediterranean woods
Quantification of the carbonaceous matter origin in submicron marine aerosol by 13C and 14C isotope analysis
Temporal and spatial variability of the stable isotopic composition of atmospheric molecular hydrogen: observations at six EUROHYDROS stations
Continuous isotopic composition measurements of tropospheric CO2 at Jungfraujoch (3580 m a.s.l.), Switzerland: real-time observation of regional pollution events
Anthropogenic imprints on nitrogen and oxygen isotopic composition of precipitation nitrate in a nitrogen-polluted city in southern China
Analysis of 13C and 18O isotope data of CO2 in CARIBIC aircraft samples as tracers of upper troposphere/lower stratosphere mixing and the global carbon cycle
Tracing the fate of atmospheric nitrate deposited onto a forest ecosystem in Eastern Asia using Δ17O
Photolysis imprint in the nitrate stable isotope signal in snow and atmosphere of East Antarctica and implications for reactive nitrogen cycling
Sources and transport of Δ14C in CO2 within the Mexico City Basin and vicinity
Pete D. Akers, Ben G. Kopec, Kyle S. Mattingly, Eric S. Klein, Douglas Causey, and Jeffrey M. Welker
Atmos. Chem. Phys., 20, 13929–13955, https://doi.org/10.5194/acp-20-13929-2020, https://doi.org/10.5194/acp-20-13929-2020, 2020
Short summary
Short summary
Water vapor isotopes recorded for 2 years in coastal northern Greenland largely reflect changes in sea ice cover, with distinct values when Baffin Bay is ice covered in winter vs. open in summer. Resulting changes in moisture transport, surface winds, and air temperature also modify the isotopes. Local glacial ice may thus preserve past changes in the Baffin Bay sea ice extent, and this will help us better understand how the Arctic environment and water cycle responds to global climate change.
Ben Yu, Lin Yang, Linlin Wang, Hongwei Liu, Cailing Xiao, Yong Liang, Qian Liu, Yongguang Yin, Ligang Hu, Jianbo Shi, and Guibin Jiang
Atmos. Chem. Phys., 20, 9713–9723, https://doi.org/10.5194/acp-20-9713-2020, https://doi.org/10.5194/acp-20-9713-2020, 2020
Short summary
Short summary
We found that Br atoms in the marine boundary layer are the most probable oxidizer that transform gaseous elemental mercury into gaseous oxidized mercury, according to the mercury isotopes in the total gaseous mercury. On the other hand, Br or Cl atoms are not the primary oxidizers that produced oxidized mercury on particles. This study showed that mercury isotopes can provide new evidence that help us to fully understand the transformations of atmospheric mercury.
Longfei Yu, Eliza Harris, Stephan Henne, Sarah Eggleston, Martin Steinbacher, Lukas Emmenegger, Christoph Zellweger, and Joachim Mohn
Atmos. Chem. Phys., 20, 6495–6519, https://doi.org/10.5194/acp-20-6495-2020, https://doi.org/10.5194/acp-20-6495-2020, 2020
Short summary
Short summary
We observed the isotopic composition of nitrous oxide in the unpolluted air at Jungfraujoch for 5 years. Our results indicate a clear seasonal pattern in the isotopic composition, corresponding with that in atmospheric nitrous oxide levels. This is most likely due to temporal variations in both emission processes and air mass sources for Jungfraujoch. Our findings are of importance to global nitrous oxide modelling and to better understanding of long-term trends in atmospheric nitrous oxide.
V. Holly L. Winton, Alison Ming, Nicolas Caillon, Lisa Hauge, Anna E. Jones, Joel Savarino, Xin Yang, and Markus M. Frey
Atmos. Chem. Phys., 20, 5861–5885, https://doi.org/10.5194/acp-20-5861-2020, https://doi.org/10.5194/acp-20-5861-2020, 2020
Short summary
Short summary
The transfer of the nitrogen stable isotopic composition in nitrate between the air and snow at low accumulation sites in Antarctica leaves an UV imprint in the snow. Quantifying how nitrate isotope values change allows us to interpret longer ice core records. Based on nitrate observations and modelling at Kohnen, East Antarctica, the dominant factors controlling the nitrate isotope signature in deep snow layers are the depth of light penetration into the snowpack and the snow accumulation rate.
Isabelle Genot, David Au Yang, Erwan Martin, Pierre Cartigny, Erwann Legendre, and Marc De Rafelis
Atmos. Chem. Phys., 20, 4255–4273, https://doi.org/10.5194/acp-20-4255-2020, https://doi.org/10.5194/acp-20-4255-2020, 2020
Short summary
Short summary
Given their critical impact on radiative forcing, sulfate aerosols have been extensively studied using their isotope signatures (δ34S, ∆33S, ∆36S, δ18O, and ∆17O). A striking observation is that ∆33S > 0 ‰, implying a missing reservoir in the sulfur cycle. Here, we measured ∆33S < 0 ‰ in black crust sulfates (i.e., formed on carbonate walls) that must therefore result from distinct chemical pathway(s) compared to sulfate aerosols, and they may well represent this complementary reservoir.
Angelina Wenger, Katherine Pugsley, Simon O'Doherty, Matt Rigby, Alistair J. Manning, Mark F. Lunt, and Emily D. White
Atmos. Chem. Phys., 19, 14057–14070, https://doi.org/10.5194/acp-19-14057-2019, https://doi.org/10.5194/acp-19-14057-2019, 2019
Short summary
Short summary
We present 14CO2 observations at a background site in Ireland and a tall tower site in the UK. These data have been used to calculate the contribution of fossil fuel sources to atmospheric CO2 mole fractions from the UK and Ireland. 14CO2 emissions from nuclear industry sites in the UK cause a higher uncertainty in the results compared to observations in other locations. The observed ffCO2 at the site was not significantly different from simulated values based on the bottom-up inventory.
Isaac J. Vimont, Jocelyn C. Turnbull, Vasilii V. Petrenko, Philip F. Place, Colm Sweeney, Natasha Miles, Scott Richardson, Bruce H. Vaughn, and James W. C. White
Atmos. Chem. Phys., 19, 8547–8562, https://doi.org/10.5194/acp-19-8547-2019, https://doi.org/10.5194/acp-19-8547-2019, 2019
Short summary
Short summary
Stable isotopes of Carbon Monoxide (CO) and radiocarbon carbon dioxide were measured over three summers at Indianapolis, Indiana, US, and for 1 year at a site thought to be strongly influenced by CO from oxidized volatile organic compounds (VOCs) in South Carolina, US. The Indianapolis results were used to provide an estimate of the carbon and oxygen isotopic signatures of CO produced from oxidized VOCs. This updated estimate agrees well with the data from South Carolina during the summer.
David Au Yang, Pierre Cartigny, Karine Desboeufs, and David Widory
Atmos. Chem. Phys., 19, 3779–3796, https://doi.org/10.5194/acp-19-3779-2019, https://doi.org/10.5194/acp-19-3779-2019, 2019
Short summary
Short summary
Sulfates present in urban aerosols collected worldwide usually exhibit 33S-anomalies whose origin remains unclear. Besides, the sulfate concentration is not very well modelled nowadays, which, coupled with the isotopic composition anomaly on the 33S, would highlight the presence of at least an additional oxidation pathway, different from O2+TMI, O3, OH, H2O2 and NO2. We suggest here the implication of two other possible oxidation pathways.
Martine M. Savard, Amanda S. Cole, Robert Vet, and Anna Smirnoff
Atmos. Chem. Phys., 18, 10373–10389, https://doi.org/10.5194/acp-18-10373-2018, https://doi.org/10.5194/acp-18-10373-2018, 2018
Short summary
Short summary
Improving air quality requires understanding of the atmospheric processes transforming nitrous oxides emitted by human activities into nitrates, an N form that may degrade natural ecosystems. Isotopes (∆17O, δ18O) are characterized in separate wet, particulate and gaseous nitrates for the first time. The gas ranges are distinct from those of the other nitrates, and the plume dynamics emerge as crucial in interpreting the results, which unravel key processes behind the distribution of nitrates.
Sergey Gromov, Carl A. M. Brenninkmeijer, and Patrick Jöckel
Atmos. Chem. Phys., 18, 9831–9843, https://doi.org/10.5194/acp-18-9831-2018, https://doi.org/10.5194/acp-18-9831-2018, 2018
Short summary
Short summary
Using the observational data on 13C (CO) and 13C (CH4) from the extra-tropical Southern Hemisphere (ETSH) and EMAC model we (1) provide an independent, observation-based evaluation of Cl atom concentration variations in the ETSH throughout 1994–2000, (2) show that the role of tropospheric Cl as a sink of CH4 is seriously overestimated in the literature, (3) demonstrate that the 13C/12C ratio of CO is a sensitive indicator for the isotopic composition of reacted CH4 and therefore for its sources.
Richard P. Fiorella, Ryan Bares, John C. Lin, James R. Ehleringer, and Gabriel J. Bowen
Atmos. Chem. Phys., 18, 8529–8547, https://doi.org/10.5194/acp-18-8529-2018, https://doi.org/10.5194/acp-18-8529-2018, 2018
Short summary
Short summary
Fossil fuel combustion produces water; where fossil fuel combustion is concentrated in urban areas, this humidity source may represent ~ 10 % of total humidity. In turn, this water vapor addition may alter urban meteorology, though the contribution of combustion vapor is difficult to measure. Using stable water isotopes, we estimate that up to 16 % of urban humidity may arise from combustion when the atmosphere is stable during winter, and develop recommendations for application in other cities.
Neda Amiri, Roghayeh Ghahremaninezhad, Ofelia Rempillo, Travis W. Tokarek, Charles A. Odame-Ankrah, Hans D. Osthoff, and Ann-Lise Norman
Atmos. Chem. Phys., 18, 7757–7780, https://doi.org/10.5194/acp-18-7757-2018, https://doi.org/10.5194/acp-18-7757-2018, 2018
David M. Nelson, Urumu Tsunogai, Dong Ding, Takuya Ohyama, Daisuke D. Komatsu, Fumiko Nakagawa, Izumi Noguchi, and Takashi Yamaguchi
Atmos. Chem. Phys., 18, 6381–6392, https://doi.org/10.5194/acp-18-6381-2018, https://doi.org/10.5194/acp-18-6381-2018, 2018
Short summary
Short summary
Atmospheric nitrate may be produced locally and/or come from upwind regions. To address this issue we measured oxygen and nitrogen isotopes of wet and dry nitrate deposition at nearby urban and rural sites. Our results suggest that, relative to nitrate in wet deposition in urban environments and wet and dry deposition in rural environments, nitrate in dry deposition in urban environments results from local NOx emissions more so than wet deposition, which is transported longer distances.
Pengzhen He, Becky Alexander, Lei Geng, Xiyuan Chi, Shidong Fan, Haicong Zhan, Hui Kang, Guangjie Zheng, Yafang Cheng, Hang Su, Cheng Liu, and Zhouqing Xie
Atmos. Chem. Phys., 18, 5515–5528, https://doi.org/10.5194/acp-18-5515-2018, https://doi.org/10.5194/acp-18-5515-2018, 2018
Short summary
Short summary
We use observations of the oxygen isotopic composition of sulfate aerosol as a fingerprint to quantify various sulfate formation mechanisms during pollution events in Beijing, China. We found that heterogeneous reactions on aerosols dominated sulfate production in general; however, in-cloud reactions would dominate haze sulfate production when cloud liquid water content was high. The findings also suggest the heterogeneity of aerosol acidity should be parameterized in models.
Tesfaye A. Berhanu, Sönke Szidat, Dominik Brunner, Ece Satar, Rüdiger Schanda, Peter Nyfeler, Michael Battaglia, Martin Steinbacher, Samuel Hammer, and Markus Leuenberger
Atmos. Chem. Phys., 17, 10753–10766, https://doi.org/10.5194/acp-17-10753-2017, https://doi.org/10.5194/acp-17-10753-2017, 2017
Short summary
Short summary
Fossil fuel CO2 is the major contributor of anthropogenic CO2 in the atmosphere, and accurate quantification is essential to better understand the carbon cycle. Such accurate quantification can be conducted based on radiocarbon measurements. In this study, we present radiocarbon measurements from a tall tower site in Switzerland. From these measurements, we have observed seasonally varying fossil fuel CO2 contributions and a biospheric CO2 component that varies diurnally and seasonally.
Markella Prokopiou, Patricia Martinerie, Célia J. Sapart, Emmanuel Witrant, Guillaume Monteil, Kentaro Ishijima, Sophie Bernard, Jan Kaiser, Ingeborg Levin, Thomas Blunier, David Etheridge, Ed Dlugokencky, Roderik S. W. van de Wal, and Thomas Röckmann
Atmos. Chem. Phys., 17, 4539–4564, https://doi.org/10.5194/acp-17-4539-2017, https://doi.org/10.5194/acp-17-4539-2017, 2017
Short summary
Short summary
Nitrous oxide is the third most important anthropogenic greenhouse gas with an increasing mole fraction. To understand its natural and anthropogenic sources
we employ isotope measurements. Results show that while the N2O mole fraction increases, its heavy isotope content decreases. The isotopic changes observed underline the dominance of agricultural emissions especially at the early part of the record, whereas in the later decades the contribution from other anthropogenic sources increases.
Giulia Zazzeri, Dave Lowry, Rebecca E. Fisher, James L. France, Mathias Lanoisellé, Bryce F. J. Kelly, Jaroslaw M. Necki, Charlotte P. Iverach, Elisa Ginty, Miroslaw Zimnoch, Alina Jasek, and Euan G. Nisbet
Atmos. Chem. Phys., 16, 13669–13680, https://doi.org/10.5194/acp-16-13669-2016, https://doi.org/10.5194/acp-16-13669-2016, 2016
Short summary
Short summary
Methane emissions estimates from the coal sector are highly uncertain. Precise δ13C isotopic signatures of methane sources can be used in atmospheric models for a methane budget assessment. Emissions from both underground and opencast coal mines in the UK, Australia and Poland were sampled and isotopically characterised using high-precision measurements of δ13C values. Representative isotopic signatures were provided, taking into account specific ranks of coal and mine type.
Qiang Huang, Jiubin Chen, Weilin Huang, Pingqing Fu, Benjamin Guinot, Xinbin Feng, Lihai Shang, Zhuhong Wang, Zhongwei Wang, Shengliu Yuan, Hongming Cai, Lianfang Wei, and Ben Yu
Atmos. Chem. Phys., 16, 11773–11786, https://doi.org/10.5194/acp-16-11773-2016, https://doi.org/10.5194/acp-16-11773-2016, 2016
Short summary
Short summary
Atmospheric airborne mercury is of particular concern because, once inhaled, both Hg and its vectors might have adverse effects on human beings. In this study, we attempted to identify the sources of PM2.5-Hg in Beijing, China, using Hg isotopic composition. Large range and seasonal variations in both mass-dependent and mass-independent fractionations of Hg isotopes in haze particles demonstrate the usefulness of Hg isotopes for directly tracing the sources and its vectors in the atmosphere.
Qianjie Chen, Lei Geng, Johan A. Schmidt, Zhouqing Xie, Hui Kang, Jordi Dachs, Jihong Cole-Dai, Andrew J. Schauer, Madeline G. Camp, and Becky Alexander
Atmos. Chem. Phys., 16, 11433–11450, https://doi.org/10.5194/acp-16-11433-2016, https://doi.org/10.5194/acp-16-11433-2016, 2016
Short summary
Short summary
The formation mechanisms of sulfate in the marine boundary layer are not well understood, which could result in large uncertainties in aerosol radiative forcing. We measure the oxygen isotopic composition (Δ17O) of sulfate collected in the MBL and analyze with a global transport model. Our results suggest that 33–50 % of MBL sulfate is formed via oxidation of S(IV) by hypohalous acids HOBr / HOCl in the aqueous phase, and the daily-mean HOBr/HOCl concentrations are on the order of 0.01–0.1 ppt.
Thomas Röckmann, Simon Eyer, Carina van der Veen, Maria E. Popa, Béla Tuzson, Guillaume Monteil, Sander Houweling, Eliza Harris, Dominik Brunner, Hubertus Fischer, Giulia Zazzeri, David Lowry, Euan G. Nisbet, Willi A. Brand, Jaroslav M. Necki, Lukas Emmenegger, and Joachim Mohn
Atmos. Chem. Phys., 16, 10469–10487, https://doi.org/10.5194/acp-16-10469-2016, https://doi.org/10.5194/acp-16-10469-2016, 2016
Short summary
Short summary
A dual isotope ratio mass spectrometric system (IRMS) and a quantum cascade laser absorption spectroscopy (QCLAS)-based technique were deployed at the Cabauw experimental site for atmospheric research (CESAR) in the Netherlands and performed in situ, high-frequency (approx. hourly) measurements for a period of more than 5 months, yielding a combined dataset with more than 2500 measurements of both δ13C and δD.
Joël Savarino, William C. Vicars, Michel Legrand, Suzanne Preunkert, Bruno Jourdain, Markus M. Frey, Alexandre Kukui, Nicolas Caillon, and Jaime Gil Roca
Atmos. Chem. Phys., 16, 2659–2673, https://doi.org/10.5194/acp-16-2659-2016, https://doi.org/10.5194/acp-16-2659-2016, 2016
Short summary
Short summary
Atmospheric nitrate is collected on the East Antarctic ice sheet. Nitrogen and oxygen stable isotopes and concentrations of nitrate are measured. Using a box model, we show that there is s systematic discrepancy between observations and model results. We suggest that this discrepancy probably results from unknown NOx chemistry above the Antarctic ice sheet. However, possible misconception in the stable isotope mass balance is not completely excluded.
T. A. Berhanu, J. Savarino, J. Erbland, W. C. Vicars, S. Preunkert, J. F. Martins, and M. S. Johnson
Atmos. Chem. Phys., 15, 11243–11256, https://doi.org/10.5194/acp-15-11243-2015, https://doi.org/10.5194/acp-15-11243-2015, 2015
Short summary
Short summary
In this field study at Dome C, Antarctica, we investigated the effect of solar UV photolysis on the stable isotopes of nitrate in snow via comparison of two identical snow pits while exposing only one to solar UV. From the difference between the average isotopic fractionations calculated for each pit, we determined a purely photolytic nitrogen isotopic fractionation of -55.8‰, in good agreement with what has been recently determined in a laboratory study.
M. Saccon, A. Kornilova, L. Huang, S. Moukhtar, and J. Rudolph
Atmos. Chem. Phys., 15, 10825–10838, https://doi.org/10.5194/acp-15-10825-2015, https://doi.org/10.5194/acp-15-10825-2015, 2015
E. D. Sofen, B. Alexander, E. J. Steig, M. H. Thiemens, S. A. Kunasek, H. M. Amos, A. J. Schauer, M. G. Hastings, J. Bautista, T. L. Jackson, L. E. Vogel, J. R. McConnell, D. R. Pasteris, and E. S. Saltzman
Atmos. Chem. Phys., 14, 5749–5769, https://doi.org/10.5194/acp-14-5749-2014, https://doi.org/10.5194/acp-14-5749-2014, 2014
J. Wintel, E. Hösen, R. Koppmann, M. Krebsbach, A. Hofzumahaus, and F. Rohrer
Atmos. Chem. Phys., 13, 11059–11071, https://doi.org/10.5194/acp-13-11059-2013, https://doi.org/10.5194/acp-13-11059-2013, 2013
F. A. Haumann, A. M. Batenburg, G. Pieterse, C. Gerbig, M. C. Krol, and T. Röckmann
Atmos. Chem. Phys., 13, 9401–9413, https://doi.org/10.5194/acp-13-9401-2013, https://doi.org/10.5194/acp-13-9401-2013, 2013
C. J. Sapart, P. Martinerie, E. Witrant, J. Chappellaz, R. S. W. van de Wal, P. Sperlich, C. van der Veen, S. Bernard, W. T. Sturges, T. Blunier, J. Schwander, D. Etheridge, and T. Röckmann
Atmos. Chem. Phys., 13, 6993–7005, https://doi.org/10.5194/acp-13-6993-2013, https://doi.org/10.5194/acp-13-6993-2013, 2013
J. Erbland, W. C. Vicars, J. Savarino, S. Morin, M. M. Frey, D. Frosini, E. Vince, and J. M. F. Martins
Atmos. Chem. Phys., 13, 6403–6419, https://doi.org/10.5194/acp-13-6403-2013, https://doi.org/10.5194/acp-13-6403-2013, 2013
A. Guillon, K. Le Ménach, P.-M. Flaud, N. Marchand, H. Budzinski, and E. Villenave
Atmos. Chem. Phys., 13, 2703–2719, https://doi.org/10.5194/acp-13-2703-2013, https://doi.org/10.5194/acp-13-2703-2013, 2013
D. Ceburnis, A. Garbaras, S. Szidat, M. Rinaldi, S. Fahrni, N. Perron, L. Wacker, S. Leinert, V. Remeikis, M. C. Facchini, A. S. H. Prevot, S. G. Jennings, M. Ramonet, and C. D. O'Dowd
Atmos. Chem. Phys., 11, 8593–8606, https://doi.org/10.5194/acp-11-8593-2011, https://doi.org/10.5194/acp-11-8593-2011, 2011
A. M. Batenburg, S. Walter, G. Pieterse, I. Levin, M. Schmidt, A. Jordan, S. Hammer, C. Yver, and T. Röckmann
Atmos. Chem. Phys., 11, 6985–6999, https://doi.org/10.5194/acp-11-6985-2011, https://doi.org/10.5194/acp-11-6985-2011, 2011
B. Tuzson, S. Henne, D. Brunner, M. Steinbacher, J. Mohn, B. Buchmann, and L. Emmenegger
Atmos. Chem. Phys., 11, 1685–1696, https://doi.org/10.5194/acp-11-1685-2011, https://doi.org/10.5194/acp-11-1685-2011, 2011
Y. T. Fang, K. Koba, X. M. Wang, D. Z. Wen, J. Li, Y. Takebayashi, X. Y. Liu, and M. Yoh
Atmos. Chem. Phys., 11, 1313–1325, https://doi.org/10.5194/acp-11-1313-2011, https://doi.org/10.5194/acp-11-1313-2011, 2011
S. S. Assonov, C. A. M. Brenninkmeijer, T. J. Schuck, and P. Taylor
Atmos. Chem. Phys., 10, 8575–8599, https://doi.org/10.5194/acp-10-8575-2010, https://doi.org/10.5194/acp-10-8575-2010, 2010
U. Tsunogai, D. D. Komatsu, S. Daita, G. A. Kazemi, F. Nakagawa, I. Noguchi, and J. Zhang
Atmos. Chem. Phys., 10, 1809–1820, https://doi.org/10.5194/acp-10-1809-2010, https://doi.org/10.5194/acp-10-1809-2010, 2010
M. M. Frey, J. Savarino, S. Morin, J. Erbland, and J. M. F. Martins
Atmos. Chem. Phys., 9, 8681–8696, https://doi.org/10.5194/acp-9-8681-2009, https://doi.org/10.5194/acp-9-8681-2009, 2009
S. A. Vay, S. C. Tyler, Y. Choi, D. R. Blake, N. J. Blake, G. W. Sachse, G. S. Diskin, and H. B. Singh
Atmos. Chem. Phys., 9, 4973–4985, https://doi.org/10.5194/acp-9-4973-2009, https://doi.org/10.5194/acp-9-4973-2009, 2009
Cited articles
Alexander, B., Hastings, M. G., Allman, D. J., Dachs, J., Thornton, J. A., and Kunasek, S. A.: Quantifying atmospheric nitrate formation pathways based on a global model of the oxygen isotopic composition (Δ17O) of atmospheric nitrate, Atmos. Chem. Phys., 9, 5043–5056, https://doi.org/10.5194/acp-9-5043-2009, 2009.
Amrani, A., Said-Ahmad, W., Shaked, Y., and Kiene, R. P.: Sulfur isotope homogeneity of oceanic DMSP and DMS, P. Natl. Acad. Sci. USA, 110, 18413–18418, 2013.
Barkan, E. and Luz, B.: High-precision measurements of 17O/16O and 18O/16O ratios in O2 and O2/Ar ratio, Rapid Commun. Mass Sp., 17, 2804–2814, 2003.
Barkan, E. and Luz, B.: High-precision measurements of 17O/16O and 18O/16O ratios in H2O, Rapid Commun. Mass Sp., 19, 3737–3742, 2005.
Bhattacharya, S. K., Pandey, A., and Savarino, J.: Determination of intramolecular isotope distribution of ozone by oxidation reaction with silver metal, J. Geophys. Res., 113, D03303, https://doi.org/10.1029/2006jd008309, 2008.
Casciotti, K. L., Sigman, D. M., Galanter Hastings, M., Böhlke, J. K., and Hilkert, A.: Measurement of the oxygen isotopic composition of nitrate in seawater and freshwater using the denitrifier method, Anal. Chem., 74, 4905–4912, 2002.
Chen, G., Davis, D., Crawford, J., Nowak, J. B., Eisele, F., Mauldin, R. L., Tanner, D., Buhr, M., Shetter, R., Lefer, B., Arimoto, R., Hogan, A., and Blake, D.: An investigation of South Pole HOx chemistry: comparison of model results with ISCAT observations, Geophys. Res. Lett., 28, 3633–3636, 2001.
Chen, Q., Geng, L., Schmidt, J. A., Xie, Z., Kang, H., Dachs, J., Cole-Dai, J., Schauer, A. J., Camp, M. G., and Alexander, B.: Isotopic constraints on the role of hypohalous acids in sulfate aerosol formation in the remote marine boundary layer, Atmos. Chem. Phys., 16, 11433–11450, https://doi.org/10.5194/acp-16-11433-2016, 2016.
Crawford, J. H., Davis, D. D., Chen, G., Buhr, M., Oltmans, S., Weller, R., Mauldin, L., Eisele, F., Shetter, R., Lefer, B., Arimoto, R., and Hogan, A.: Evidence for photochemical production of ozone at the South Pole surface, Geophys. Res. Lett., 28, 3641–3644, 2001.
Davis, D., Nowak, J. B., Chen, G., Buhr, M., Arimoto, R., Hogan, A., Eisele, F., Mauldin, L., Tanner, D., Shetter, R., Lefer, B., and McMurry, P.: Unexpected high levels of NO observed at South Pole, Geophys. Res. Lett., 28, 3625–3628, 2001.
Erbland, J., Vicars, W. C., Savarino, J., Morin, S., Frey, M. M., Frosini, D., Vince, E., and Martins, J. M. F.: Air-snow transfer of nitrate on the East Antarctic Plateau – Part 1: Isotopic evidence for a photolytically driven dynamic equilibrium in summer, Atmos. Chem. Phys., 13, 6403–6419, https://doi.org/10.5194/acp-13-6403-2013, 2013.
Feitcher, J., Kjellstrom, E., Rodhe, H., Dentener, F., Lelieveld, J., and Roelofs, G. J.: Simulation of the tropospheric sulfur cycle in a global climate model, Atmos. Environ., 30, 1693–1707, 1996.
Fogelman, K. D., Walker, D. M., and Margerum, D. W.: Nonmetal redox kinetics: hypochlorite and hypochlorous acid reactions with sulfite, Inorg. Chem., 28, 986–993, https://doi.org/10.1021/ic00305a002, 1989.
Frey, M. M., Savarino, J., Morin, S., Erbland, J., and Martins, J. M. F.: Photolysis imprint in the nitrate stable isotope signal in snow and atmosphere of East Antarctica and implications for reactive nitrogen cycling, Atmos. Chem. Phys., 9, 8681–8696, https://doi.org/10.5194/acp-9-8681-2009, 2009.
Frey, M. M., Roscoe, H. K., Kukui, A., Savarino, J., France, J. L., King, M. D., Legrand, M., and Preunkert, S.: Atmospheric nitrogen oxides (NO and NO2) at Dome C, East Antarctica, during the OPALE campaign, Atmos. Chem. Phys., 15, 7859–7875, https://doi.org/10.5194/acp-15-7859-2015, 2015.
Gao, Y. Q. and Marcus, R. A.: Strange and unconventional isotope effects in ozone formation, Science, 293, 259–263, 2001
Geng, L., Schauer, A. J., Kunasek, S. A., Sofen, E. D., Erbland, J., Savarino, J., Allman, D. J., Sletten, R. S., and Alexander, B.: Analysis of oxygen-17 excess of nitrate and sulfate at sub-micromole levels using the pyrolysis method, Rapid Commun. Mass Sp., 27, 2411–2419, 2013.
Granger, J. and Sigman, D. M.: Removal of nitrite with sulfamic acid for nitrate N and O isotope analysis with the denitrifier method, Rapid Commun. Mass Sp., 23, 3753–3762, 2009.
Grilli, R., Legrand, M., Kukui, A., Mejean, G., Preunkert, S., and Romanini, D.: First investigations of IO, BrO, and NO2 summer atmospheric levels at a coastal East Antarctic site using mode-locked cavity enhanced absorption spectroscopy, Geophys. Res. Lett., 40, 791–796, 2013
Hattori, S., Toyoda, A., Toyoda, S., Ishino S., Ueno, Y., and Yoshida, N.: Determination of the sulfur isotope ratio in carbonyl sulfide using gas chromatography/isotope ratio mass spectrometry on fragment ions 32S+, 33S+, and 34S, Anal. Chem., 87, 477–484, 2015.
Hill-Falkenthal, J., Priyadarshi, A., Savarino, J., and Thiemens, M.: Seasonal variations in 35S and Δ17O of sulfate aerosols on the Antarctic plateau, J. Geophys. Res. Atmos., 118, 9444–9455, 2013.
Holland, H. D., Lazar, B., and McCaffrey, M.: Evolution of atmosphere and oceans, Nature, 320, 27–33, 1986.
Holt, B. D., Cunningham, P. T., Engelkemeir, A. G., Graczyk, D. G., and Kumar, R.: Oxygen-18 study of nonaqueous-phase oxidation of sulfur dioxide, Atmos. Env., 17, 625–632, 1983.
Janssen, C. and Tuzson, B.: A diode laser spectrometer for symmetry selective detection of ozone isotopomers, Appl. Phys. B, 82, 487–494, 2006.
Jefferson, A., Tanner, D. J., Eisele, F. L., Davis, D. D., Chen, G., Crawford, J., Huey, J. W., Torres, A. L., and Berresheim, H.: OH photochemistry and methane sulfonic acid formation in the coastal Antarctic boundary layer, J. Geophys. Res., 103, 1647–1656, 1998.
Johnston, J. C. and Thiemens, M. H.: The isotopic compo- sition of tropospheric ozone in three environments, J. Geophys. Res. Atmos., 102, 25395–25404, 1997.
Jourdain, B. and Legrand, M.: Year-round records of bulk and size-segregated aerosol composition and HCl and HNO3 levels in the Dumont d'Urville (coastal Antarctica) atmosphere: Implications for sea-salt aerosol fractionation in the winter and summer, J. Geophys. Res., 107, 4645, https://doi.org/10.1029/2002JD002471, 2002.
Kaleschke, L., Lupkes, C., Vihma, T., Haarpaintner, J., Bochert, A., Hartmann, J., and Heygster G.: SSM/I sea ice remote sensing for mesoscale ocean-atmosphere interaction analysis, Can. J. Remote Sens., 27, 526–537, 2001.
Konig-Langlo, G., King, J. C., and Pettre, P.: Climatology of the three coastal Antarctic stations Dumont d'Urville, Neumayer, and Halley, J. Geophys. Res., 103, 10935–10946, 1998.
Krankowsky, D., Bartecki, F., Klees, G. G., Mauersberger, K., Schellenbach, K., and Stehr, J.: Measurement of heavy isotope enrichment in tropospheric ozone, Geophys. Res. Lett., 22, 1713–1716, 1995.
Kukui, A., Legrand, M., Ancellet, G., Gros, V., Bekki, S., Sarda-Esteve, R., Loisil, R., and Preunkert, S.: Measurements of OH and RO2 radicals at the coastal Antarctic site of Dumont d'Urville (East Antarctica) in summer 2010–2011, J. Geophys. Res.-Atmos., 117, D12310, https://doi.org/10.1029/2012JD017614, 2012.
Kukui, A., Legrand, M., Preunkert, S., Frey, M. M., Loisil, R., Gil Roca, J., Jourdain, B., King, M. D., France, J. L., and Ancellet, G.: Measurements of OH and RO2 radicals at Dome C, East Antarctica, Atmos. Chem. Phys., 14, 12373–12392, https://doi.org/10.5194/acp-14-12373-2014, 2014.
Lee, C. C. W. and Thiemens, M. H.: The measurements of atmospheric sulfate from a coastal and high alpine region:A mass-indepent isotopic anomaly, J. Geophys. Res., 106, 17359–17373, 2001.
Legrand, M., Preunkert, S., Jourdain, B., Gallée, H., Goutail, F., Weller, R., and Savarino, J.: Year-round record of surface ozone at coastal (Dumont d'Urville) and inland (Concordia) sites in East Antarctica, J. Geophys. Res., 114, D20306, https://doi.org/10.1029/2008JD011667, 2009.
Legrand, M., Preunkert, S., Savarino, J., Frey, M. M., Kukui, A., Helmig, D., Jourdain, B., Jones, A. E., Weller, R., Brough, N., and Gallée, H.: Inter-annual variability of surface ozone at coastal (Dumont d'Urville, 2004–2014) and inland (Concordia, 2007–2014) sites in East Antarctica, Atmos. Chem. Phys., 16, 8053–8069, https://doi.org/10.5194/acp-16-8053-2016, 2016a.
Legrand, M., Yang, X., Preunkert, S., and Theys, N.: Year-round records of sea salt, gaseous, and particulate inorganic bromine in the atmospheric boundary layer at coastal (Dumont d'Urville) and central (Concordia) East Antarctic sites, J. Geophys. Res. Atmos., 121, 997–1023, https://doi.org/10.1002/2015JD024066, 2016b.
Li, X., Bao, H., Gan, Y., Zhou, A., and Liu, Y.: Multiple oxygen and sulfur isotope compositions of secondary atmospheric sulfate in a mega-city in central China, Atmos. Environ., 81, 591–599, 2013.
Matsuhisa, Y., Goldsmith, J. R., and Clayton, R. N.: Mechanisms of hydrothermal crystallization of quartz at 250 °C and 15 kbar, Geochim. Cosmochim. Ac., 42, 173–182, 1978.
McCabe, J. R., Savarino, J., Alexander, B., Gong, S., and Thiemens, M. H.: Isotopic constraints on non-photochemical sulfate production in the Arctic winter, Geophys. Res. Lett., 33, L05810, https://doi.org/10.1029/2005GL025164, 2006.
Michalski, G., Scott, Z., Kabiling, M., and Thiemens, M. H.: First measurements and modeling of Δ17O in atmospheric nitrate, Geophys. Res. Lett., 30, 1870, https://doi.org/10.1029/2003GL017015, 2003.
Minikin, A., Legrand, M., Hall, J., Wagenbach, D., Kleefeld, C., Wolff, E., Pasteur, E. C., and Ducroz, F.: Sulfur-containing species (sulfate and methanesulfonate) in coastal Antarctic aerosol and precipitation, J. Geophys. Res., 103, 10975–10990, 1998.
Morin, S., Savarino, J., Bekki, S., Gong, S., and Bottenheim, J. W.: Signature of Arctic surface ozone depletion events in the isotope anomaly (Δ17O) of atmospheric nitrate, Atmos. Chem. Phys., 7, 1451–1469, https://doi.org/10.5194/acp-7-1451-2007, 2007.
Morin, S., Savarino, J., Frey, M. M., Yan, N., Bekki, S., Bottenheim, J. W., and Martins, J. M. F.: Tracing the origin and fate of NOx in the Arctic atmosphere using stable isotopes in nitrate, Science, 322, 730–732, https://doi.org/10.1126/science.1161910, 2008.
Morin, S., Savarino, J., Frey, M. M., Domine, F., Jacobi, H. W., Kaleschke, L., and Martins, J. M. F.: Comprehensive isotopic composition of atmospheric nitrate in the Atlantic Ocean boundary layer from 65° S to 79° N, J. Geophys. Res., 114, D05303, https://doi.org/10.1029/2008JD010696, 2009.
Morin, S., Sander, R., and Savarino, J.: Simulation of the diurnal variations of the oxygen isotope anomaly (Δ17O) of reactive atmospheric species, Atmos. Chem. Phys., 11, 3653–3671, https://doi.org/10.5194/acp-11-3653-2011, 2011.
Oduro, H., Van Alstyne, K. L., and Farquhar, J.: Sulfur isotope variability of oceanic DMSP generation and its contributions to marine biogenic sulfur emissions, P. Natl. Acad. Sci. USA, 109, 9012–9016, 2012.
Preunkert, S., Legrand, M., Jourdain, B., Moulin, C., Belviso, S., Kasamatsu, N., Fukuchi, M., and Hirawake, T.: Interannual variability of dimethylsulfide in air and seawater and its atmospheric oxidation by-products (methanesulfonate and sulfate) at Dumont d'Urville, coastal Antarctica (1999–2003), J. Geophys. Res., 112, D06306, https://doi.org/10.1029/2006JD007585, 2007.
Preunkert, S., Jourdain, B., Legrand, M., Udisti, R., Becagli, S., and Cerri, O.: Seasonality of sulfur species (sulfate, methanesulfonate and dimethyl sulfur) in Antarctica: inland versus coastal regions, J. Geophys. Res., 113, D15302, https://doi.org/10.1029/2008JD009937, 2008.
Santacesaria, V., MacKenzie, A. R., and Stefanutti, L.: A climatological study of polar stratospheric clouds (1989–1997) from LIDAR measurements over Dumont d'Urville (Antarctica), Tellus, 53B, 306–321, 2001.
Savarino, J. and Thiemens, M. H.: Analytical procedure to determine both δ18O and δ17O of H2O2 in natural water and first measurements, Atmos. Environ., 33, 3683–3690, 1999.
Savarino, J., Lee, C. C. W., and Thiemens, M. H.: Laboratory oxygen isotopic study of sulfur (IV) oxidation: Origin of the mass-independent oxygen isotopic anomaly in atmospheric sulfates and sulfate mineral deposits on Earth, J. Geophys. Res., 105, 29079–29088. 2000.
Savarino, J., Alexander, B., Darmohusodo, V., and Thiemens, M. H.: Sulfur and oxygen isotope analysis of sulfate at micromole levels using a pyrolysis technique in a continuous flow system, Anal. Chem., 73, 4457–4462, 2001.
Savarino, J., Kaiser, J., Morin, S., Sigman, D. M., and Thiemens, M. H.: Nitrogen and oxygen isotopic constraints on the origin of atmospheric nitrate in coastal Antarctica, Atmos. Chem. Phys., 7, 1925–1945, https://doi.org/10.5194/acp-7-1925-2007, 2007.
Savarino, J., Bhattacharya, S. K., Morin, S., Baroni, M., and Doussin, J. F.: The NO + O3 reaction: a triple oxygen isotope perspective on the reaction dynamics and atmospheric implications for the transfer of the ozone isotope anomaly, J. Chem. Phys., 128, 194303, https://doi.org/10.1063/1.2917581, 2008.
Savarino, J., Morin, S., Erbland, J., Grannec, F., Patey, M. D., Vicars, W., Alexander, B., and Achterberg, E. P.: Isotopic composition of atmospheric nitrate in a tropical marine boundary layer, P. Natl. Acad. Sci. USA, 110, 17668–17673, 2013.
Savarino, J., Vicars, W. C., Legrand, M., Preunkert, S., Jourdain, B., Frey, M. M., Kukui, A., Caillon, N., and Gil Roca, J.: Oxygen isotope mass balance of atmospheric nitrate at Dome C, East Antarctica, during the OPALE campaign, Atmos. Chem. Phys., 16, 2659–2673, https://doi.org/10.5194/acp-16-2659-2016, 2016.
Schauer, A. J., Kunasek, S. A., Sofen, E. D., Erbland, J., Savarino, J., Johnson, B. W., Amos, H. M., Shaheen, R., Abaunza, M., Jackson, T. L., Thiemens, M. H., and Alexander, B.: Oxygen isotope exchange with quartz during pyrolysis of silver sulfate and silver nitrate, Rapid Commun. Mass Sp., 26, 2151–2157, 2012.
Seinfeld, J. H. and Pandis, S. N.: Atmospheric Chemistry and Physics, 2nd edition, Wiley & Sons, New York, USA, 2006.
Sofen, E. D., Alexander, B., and Kunasek, S. A.: The impact of anthropogenic emissions on atmospheric sulfate production pathways, oxidants, and ice core Δ17O(SO42−), Atmos. Chem. Phys., 11, 3565–3578, https://doi.org/10.5194/acp-11-3565-2011, 2011.
Stein, A. F., Draxler, R. R., Rolph, G. D., Stunder, B. J. B., Cohen, M. D., and Ngan, F.: NOAA's HYSPLIT atmospheric transport and dispersion modeling system, B. Am. Meteorol. Soc., 96, 2059–2077, https://doi.org/10.1175/BAMS-D-14-00110.1, 2015.
Troy, R. C. and Margerum, D. W.: Non-metal redox kinetics: Hypobromite and hypobromous acid reactions with iodide and with sulfite and the hydrolysis of bromosulfate, Inorg. Chem., 30, 3538–3543, https://doi.org/10.1021/ic00018a028, 1991.
Vicars, W. C. and Savarino, J.: Quantitative constraints on the 17O-excess (Δ17O) signature of surface ozone: ambient measurements from 50° N to 50° S using the nitrite-coated filter technique, Geochim. Cosmochim. Ac., 135, 270–287, 2014.
Vicars, W. C., Bhattacharya, S. K., Erbland, J., and Savarino, J.: Measurement of the 17O-excess (Δ17O) of tropospheric ozone using a nitrite-coated filter, Rapid Commun. Mass Sp., 26, 1219–1231, 2012.
von Glasow, R., Sander, R., Bott, A., and Crutzen, P. J.: Modeling halogen chemistry in the marine boundary layer. 2. Interactions with sulfur and the cloud-covered MBL, J. Geophys. Res., 107, 4323, 10.1029/2001JD000 943, 2002.
Vogt, R., Crutzen, P. J., and Sander, R.: A mechanism for halogen release from sea-salt aerosol in the remote marine boundary layer, Nature, 383, 327–330, https://doi.org/10.1038/383327a0, 1996.
Wagenbach, D., Ducroz, F., Mulvaney, R., Keck, L., Minikin, A., Legrand, M., Hall, J., and Wolff, E.: Sea-salt aerosol in coastal Antarctic regions, J. Geophys. Res., 103, 10961–10974, 1998.
Yiin, B. S. and Margerum, D. W.: Kinetics of Hydrolysis of the Chlorosulfate Ion, Inorg. Chem., 27, 1670–1672, https://doi.org/10.1021/ic00283a002, 1988.
Zatko, M., Geng, L., Alexander, B., Sofen, E., and Klein, K.: The impact of snow nitrate photolysis on boundary layer chemistry and the recycling and redistribution of reactive nitrogen across Antarctica and Greenland in a global chemical transport model, Atmos. Chem. Phys., 16, 2819–2842, https://doi.org/10.5194/acp-16-2819-2016, 2016.
Short summary
We show the first simultaneous observations of triple oxygen isotopic compositions of atmospheric sulfate, nitrate, and ozone at Dumont d'Urville, coastal Antarctica. The contrasting seasonal trends between oxygen isotopes of ozone and those of sulfate and nitrate indicate that these signatures in sulfate and nitrate are mainly controlled by changes in oxidation chemistry. We also discuss the specific oxidation chemistry induced by the unique phenomena at the site.
We show the first simultaneous observations of triple oxygen isotopic compositions of...
Altmetrics
Final-revised paper
Preprint