Articles | Volume 9, issue 22
https://doi.org/10.5194/acp-9-8681-2009
© Author(s) 2009. This work is distributed under
the Creative Commons Attribution 3.0 License.
the Creative Commons Attribution 3.0 License.
https://doi.org/10.5194/acp-9-8681-2009
© Author(s) 2009. This work is distributed under
the Creative Commons Attribution 3.0 License.
the Creative Commons Attribution 3.0 License.
16 Nov 2009
Photolysis imprint in the nitrate stable isotope signal in snow and atmosphere of East Antarctica and implications for reactive nitrogen cycling
M. M. Frey
British Antarctic Survey, Natural Environment Research Council, Cambridge, UK
Université Joseph Fourier - Grenoble 1/CNRS-INSU, Laboratoire de Glaciologie et Géophysique de l'Environnement, St. Martin d'Hères, France
J. Savarino
Université Joseph Fourier - Grenoble 1/CNRS-INSU, Laboratoire de Glaciologie et Géophysique de l'Environnement, St. Martin d'Hères, France
S. Morin
Université Joseph Fourier - Grenoble 1/CNRS-INSU, Laboratoire de Glaciologie et Géophysique de l'Environnement, St. Martin d'Hères, France
now at Météo-France/CNRS, CNRM-GAME, CEN, St. Martin d'Hères, France
J. Erbland
Université Joseph Fourier - Grenoble 1/CNRS-INSU, Laboratoire de Glaciologie et Géophysique de l'Environnement, St. Martin d'Hères, France
J. M. F. Martins
Université Joseph Fourier - Grenoble 1/CNRS-INSU/G-INP/IRD, Laboratoire d'étude des Transferts en Hydrologie et Environnement, St. Martin d'Hères, France
Related subject area
Subject: Isotopes | Research Activity: Field Measurements | Altitude Range: Troposphere | Science Focus: Chemistry (chemical composition and reactions)
Photolytic modification of seasonal nitrate isotope cycles in East Antarctica
Atmospheric methane isotopes identify inventory knowledge gaps in the Surat Basin, Australia, coal seam gas and agricultural regions
Nitrate Chemistry in the Northeast US Part II: Oxygen Isotopes Reveal Differences in Particulate and Gas Phase Formation
Nitrate chemistry in the northeast US part I: nitrogen isotope seasonality tracks nitrate formation chemistry
Methane (CH4) sources in Krakow, Poland: insights from isotope analysis
Isotopic signatures of major methane sources in the coal seam gas fields and adjacent agricultural districts, Queensland, Australia
Measurement report: Nitrogen isotopes (δ15N) and first quantification of oxygen isotope anomalies (Δ17O, δ18O) in atmospheric nitrogen dioxide
Measurement report: Spatial variability of northern Iberian rainfall stable isotope values – investigating atmospheric controls on daily and monthly timescales
Isotopic constraints on atmospheric sulfate formation pathways in the Mt. Everest region, southern Tibetan Plateau
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
Seasonal variations of triple oxygen isotopic compositions of atmospheric sulfate, nitrate, and ozone at Dumont d'Urville, coastal Antarctica
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
Sources and transport of Δ14C in CO2 within the Mexico City Basin and vicinity
Pete D. Akers, Joël Savarino, Nicolas Caillon, Olivier Magand, and Emmanuel Le Meur
Atmos. Chem. Phys., 22, 15637–15657, https://doi.org/10.5194/acp-22-15637-2022, https://doi.org/10.5194/acp-22-15637-2022, 2022
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Nitrate isotopes in Antarctic ice do not preserve the seasonal isotopic cycles of the atmosphere, which limits their use to study the past. We studied nitrate along an 850 km Antarctic transect to learn how these cycles are changed by sunlight-driven chemistry in the snow. Our findings suggest that the snow accumulation rate and other environmental signals can be extracted from nitrate with the right sampling and analytical approaches.
Bryce F. J. Kelly, Xinyi Lu, Stephen J. Harris, Bruno G. Neininger, Jorg M. Hacker, Stefan Schwietzke, Rebecca E. Fisher, James L. France, Euan G. Nisbet, David Lowry, Carina van der Veen, Malika Menoud, and Thomas Röckmann
Atmos. Chem. Phys., 22, 15527–15558, https://doi.org/10.5194/acp-22-15527-2022, https://doi.org/10.5194/acp-22-15527-2022, 2022
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This study explores using the composition of methane of in-flight atmospheric air samples for greenhouse gas inventory verification. The air samples were collected above one of the largest coal seam gas production regions in the world. Adjacent to these gas fields are coal mines, Australia's largest cattle feedlot, and over 1 million grazing cattle. The results are also used to identify methane mitigation opportunities.
Heejeong Kim, Wendell W. Walters, Claire Bekker, Lee T. Murray, and Meredith G. Hastings
Atmos. Chem. Phys. Discuss., https://doi.org/10.5194/acp-2022-622, https://doi.org/10.5194/acp-2022-622, 2022
Revised manuscript accepted for ACP
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Atmospheric nitrate has an important impact on human and ecosystem health. We evaluated atmospheric nitrate formation pathways in the northeastern U.S. utilizing oxygen isotope compositions. There was a significant difference between the phases of nitrate, indicating different formation mechanisms. Comparison of the observations with model simulations indicated that N2O5 hydrolysis was overpredicted. Our study has important implications for improving atmospheric chemistry model representation.
Claire Bekker, Wendell W. Walters, Lee T. Murray, and Meredith G. Hastings
Atmos. Chem. Phys. Discuss., https://doi.org/10.5194/acp-2022-621, https://doi.org/10.5194/acp-2022-621, 2022
Revised manuscript accepted for ACP
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Nitrate is a critical component of the atmosphere that degrades air quality and ecosystem health. We have investigated the nitrogen isotope compositions of nitrate from deposition samples collected across the northeastern United States. Spatiotemporal variability in the nitrogen isotope compositions was found to track with nitrate formation chemistry. Our results highlight that nitrogen isotope compositions may be a robust tool for improving model representation of nitrate chemistry.
Malika Menoud, Carina van der Veen, Jaroslaw Necki, Jakub Bartyzel, Barbara Szénási, Mila Stanisavljević, Isabelle Pison, Philippe Bousquet, and Thomas Röckmann
Atmos. Chem. Phys., 21, 13167–13185, https://doi.org/10.5194/acp-21-13167-2021, https://doi.org/10.5194/acp-21-13167-2021, 2021
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Using measurements of methane isotopes in ambient air and a 3D atmospheric transport model, in Krakow, Poland, we mainly detected fossil-fuel-related sources, coming from coal mining in Silesia and from the use of natural gas in the city. Emission inventories report large emissions from coal mine activity in Silesia, which is in agreement with our measurements. However, methane sources in the urban area of Krakow related to the use of fossil fuels might be underestimated in the inventories.
Xinyi Lu, Stephen J. Harris, Rebecca E. Fisher, James L. France, Euan G. Nisbet, David Lowry, Thomas Röckmann, Carina van der Veen, Malika Menoud, Stefan Schwietzke, and Bryce F. J. Kelly
Atmos. Chem. Phys., 21, 10527–10555, https://doi.org/10.5194/acp-21-10527-2021, https://doi.org/10.5194/acp-21-10527-2021, 2021
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Many coal seam gas (CSG) facilities in the Surat Basin, Australia, are adjacent to other sources of methane, including agricultural, urban, and natural seeps. This makes it challenging to estimate the amount of methane being emitted into the atmosphere from CSG facilities. This research demonstrates that measurements of the carbon and hydrogen stable isotopic composition of methane can distinguish between and apportion methane emissions from CSG facilities, cattle, and many other sources.
Sarah Albertin, Joël Savarino, Slimane Bekki, Albane Barbero, and Nicolas Caillon
Atmos. Chem. Phys., 21, 10477–10497, https://doi.org/10.5194/acp-21-10477-2021, https://doi.org/10.5194/acp-21-10477-2021, 2021
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We report an efficient method to collect atmospheric NO2 adapted for multi-isotopic analysis and present the first NO2 triple oxygen and double nitrogen isotope measurements. Atmospheric samplings carried out in Grenoble, France, highlight the NO2 isotopic signature sensitivity to the local NOx emissions and chemical regimes. These preliminary results are very promising for using the combination of Δ17O and δ15N of NO2 as a probe of the atmospheric NOx emissions and chemistry.
Ana Moreno, Miguel Iglesias, Cesar Azorin-Molina, Carlos Pérez-Mejías, Miguel Bartolomé, Carlos Sancho, Heather Stoll, Isabel Cacho, Jaime Frigola, Cinta Osácar, Arsenio Muñoz, Antonio Delgado-Huertas, Ileana Bladé, and Françoise Vimeux
Atmos. Chem. Phys., 21, 10159–10177, https://doi.org/10.5194/acp-21-10159-2021, https://doi.org/10.5194/acp-21-10159-2021, 2021
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We present a large and unique dataset of the rainfall isotopic composition at seven sites from northern Iberia to characterize their variability at daily and monthly timescales and to assess the role of climate and geographic factors in the modulation of δ18O values. We found that the origin, moisture uptake along the trajectory and type of precipitation play a key role. These results will help to improve the interpretation of δ18O paleorecords from lacustrine carbonates or speleothems.
Kun Wang, Shohei Hattori, Mang Lin, Sakiko Ishino, Becky Alexander, Kazuki Kamezaki, Naohiro Yoshida, and Shichang Kang
Atmos. Chem. Phys., 21, 8357–8376, https://doi.org/10.5194/acp-21-8357-2021, https://doi.org/10.5194/acp-21-8357-2021, 2021
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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 decipher 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 conditions of high cloud water pH.
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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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
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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, Roya Ghahreman, 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
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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
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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
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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
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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.
Sakiko Ishino, Shohei Hattori, Joel Savarino, Bruno Jourdain, Susanne Preunkert, Michel Legrand, Nicolas Caillon, Albane Barbero, Kota Kuribayashi, and Naohiro Yoshida
Atmos. Chem. Phys., 17, 3713–3727, https://doi.org/10.5194/acp-17-3713-2017, https://doi.org/10.5194/acp-17-3713-2017, 2017
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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.
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
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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
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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
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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
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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
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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
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
Anastasio, C., Galbavy, E. S., Hutterli, M. A., Burkhart, J. F., and Friel, D. K.: Photoformation of hydroxyl radical on snow grains at Summit, Greenland, Atmos. Environ., 41, 5110–5121, 2007.
Baertschi, P.: Absolute 18}{O content of the Standard Mean Ocean Water, Earth Planet. Sc. Lett., 31(3), 341–344, 1976.
Begun, G. M. and Fletcher, W. H.: Partion function ratios for molecules containing nitrogen isotopes, J. Chem. Phys., 33, 1083–1085, 1960.
Blunier, T., Floch, G. L., Jacobi, H. W., and Quansah, E.: Isotopic view on nitrate loss in A}ntarctic surface snow, Geophys. Res. Lett., 32, L13501, https://doi.org/{10.1029/2005GL023011, 2005.
B{ö}hlke, J. K., Mroczkowski, S. J., and Coplen, T. B.: Oxygen isotopes in nitrate: new reference materials for 18{O}:17{O}:16{O} measurements and observations on nitrate-water equilibration, Rapid Commun. Mass Sp., 17, 1835–1846, 2003.
Boxe, C. S. and Saiz-Lopez, A.: Multiphase modeling of nitrate photochemistry in the quasi-liquid layer (QLL): implications for NOx release from the Arctic and coastal Antarctic snowpack, Atmos. Chem. Phys., 8, 4855–4864, 2008.
Casciotti, K. L., Sigman, D. M., Hastings, M. G., Bohlke, 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.
Chu, L. and Anastasio, C.: Quantum yields of hydroxyl radical and nitrogen dioxide from the photolysis of nitrate on ice, J. Phys. Chem. A, 107, 9594–9602, 2003.
Criss, R. E.: Principles of stable isotope distribution, Oxford University Press, 1999.
Davis, D. D., Seelig, J., Huey, G., Crawford, J., Chen, G., Wang, Y. H., Buhr, M., Helmig, D., Neff, W., Blake, D., Arimoto, R., and Eisele, F.: A reassessment of A}ntarctic plateau reactive nitrogen based on {ANTCI} 2003 airborne and ground based measurements, Atmos. Environ., 42, 2831–2848, https://doi.org/{10.1016/j.atmosenv.2007.07.039, 2008.
Dery, S. J. and Yau, M. K.: Large-scale mass balance effects of blowing snow and surface sublimation, J. Geophys. Res., 107, 4679, https://doi.org/{10.1029/2001JD001251}, 2002.
Dibb, J. E. and Fahnestock, M.: Snow accumulation, surface height change, and firn densification at S}ummit, {G}reenland: Insights from 2 years of in situ observation, J. Geophys. Res., 109, D24113, https://doi.org/{10.1029/2003JD004300, 2004.
Dibb, J. E., Whitlow, S. I., and Arsenault, M.: Seasonal variations in the soluble ion content of snow at S}ummit, {G}reenland: Constraints from three years of daily surface snow samples, Atmos. Environ., 41, 5007–5019, https://doi.org/{10.1016/j.atmosenv.2006.12.010, 2007.
Dubowski, Y., Colussi, A. J. and Hoffmann, M. R.: Nitrogen dioxide release in the 302 nm band photolysis of spray-frozen aqueous nitrate solutions, Atmospheric implications, J. Phys. Chem. A, 105, 20, 4928–4932, https://doi.org/{10.1021/jp0042009}, 2001.
Floch, G.: Composition Isotopique du Nitrate dans le Névé Antarctique: Avançées et Nouvelles Perspectives sur les Phénomènes Post-dépôts, Inauguraldissertation der Philosophisch-naturwissenschaftlichen Fakultät der Universität Bern, Abteilung für Klima- und Umweltphysik, Physikalisches Institut der Universität Bern, 2006.
Frey, M. M., Stewart, R. W., McConnell, J. R., and Bales, R. C.: Atmospheric hydroperoxides in West Antarctica: links to stratospheric ozone and atmospheric oxidation capacity, J. Geophys. Res., 110, D23301, https://doi.org/{10.1029/2005JD006110}, 2005.
Frey, M. M., Bales, R. C., and McConnell, J. R.: Climate sensitivity of the century-scale hydrogen peroxide ({H}2{O}2) record preserved in 23 ice cores from W}est {A}ntarctica, J. Geophys. Res., 111, D21301, https://doi.org/{10.1029/2005JD006816, 2006.
Freyer, H. D., Kobel, K., Delmas, R. J., Kley, D., and Legrand, M. R.: First results of 15{N}/14{N} ratios in nitrate from alpine and polar ice cores, Tellus B, 48, 93–105, 1996.
Frezzotti, M., Pourchet, M., Flora, O., Gandolfi, S., Gay, M., Urbini, S., Vincent, C., Becagli, S., Gragnani, R., Proposito, M., Severi, M., Traversi, R., Udisti, R., and Fily, M.: New estimations of precipitation and surface sublimation in East Antarctica from snow accumulation measurements, Clim. Dynam., 23, 803–813, https://doi.org/{10.1007/s00382-004-0462-5}, 2004.
Gallet, J. C., Arnaud, L., and Domine, F.: Specific surface area of snow at Dome C, Antarctica. Rates of change for timescales from 1 day to 60 years, Geophys. Res. Abstr., EGU2009-4270, 2009.
Gay, M., Fily, M., Genthon, C., Frezzotti, M., Oerter, H., and Winther, J. G.: Snow grain-size measurements in Antarctica, J. Glaciol., 48(163), 527–535, 2002.
Grannas, A. M., Jones, A. E., Dibb, J., Ammann, M., Anastasio, C., Beine, H. J., Bergin, M., Bottenheim, J., Boxe, C. S., Carver, G., Chen, G., Crawford, J. H., Dominé, F., Frey, M. M., Guzmán, M. I., Heard, D. E., Helmig, D., Hoffmann, M. R., Honrath, R. E., Huey, L. G., Hutterli, M., Jacobi, H. W., Klán, P., Lefer, B., McConnell, J., Plane, J., Sander, R., Savarino, J., Shepson, P. B., Simpson, W. R., Sodeau, J. R., von Glasow, R., Weller, R., Wolff, E. W., and Zhu, T.: An overview of snow photochemistry: evidence, mechanisms and impacts, Atmos. Chem. Phys., 7, 4329–4373, 2007.
Hastings, M. G., Steig, E. J., and Sigman, D. M.: Seasonal variations in N and O isotopes of nitrate in snow at S}ummit, {G}reenland: Implications for the study of nitrate in snow and ice cores, J. Geophys. Res., 109, D20306, https://doi.org/{10.1029/2004JD004991, 2004.
Hastings, M. G., Sigman, D. M., and Steig, E. J.: Glacial/interglacial changes in the isotopes of nitrate from the G}reenland {I}ce {S}heet {P}roject 2 ({GISP}2) ice core, Global Biogeochem. Cy., 19, GB4024, https://doi.org/{10.1029/2005GB002502, 2005.
Hastings, M. G., Jarvis, J. C., and Steig, E. J.: Anthropogenic impacts on nitrogen isotopes of ice-core nitrate, Science, 324, 1288, https://doi.org/{10.1126/science.1170510}, 2009.
Hauglustaine, D. A., Granier, C., Brasseur, G. P., and Megie, G.: The importance of atmospheric chemistry in the calculation of radiative forcing on the climate system, J. Geophys. Res., 99, 1173–1186, 1994.
Heaton, T. H. E., Wynn, P., and Tye, A. M.: Low 15{N}/14{N} ratios for nitrate in snow in the H}igh {A}rctic (79° {N}), Atmos. Environ., 38, 5611–5621, https://doi.org/{10.1016/j.atmosenv.2004.06.028, 2004.
Hudson, P. K., Shilling, J. E., Tolbert, M. A., and Toon, O. B.: Uptake of nitric acid on ice at tropospheric temperatures: Implications for cirrus clouds, J. Phys. Chem. A, 106, 9874–9882, https://doi.org/{10.1021/jp020508j}, 2002.
Huey, L. G., Tanner, D. J., Slusher, D. L., Dibb, J. E., Arimoto, R., Chen, G., Davis, D., Buhr, M. P., and Nowak, J. B.: CIMS measurements of HNO3 and SO2 at the South Pole during ISCAT 2000, Atmos. Environ., 38(32), 5411–5421, https://doi.org/{10.1016/j.atmosenv.2004.04.037}, 2004.
Jacobi, H. W., Annor, T., and Quansah, E.: Investigation of the photochemical decomposition of nitrate, hydrogen peroxide, and formaldehyde in artificial snow, J. Photoch. Photobio. A, 179, 330–338, https://doi.org/{10.1016/j.jphotochem.2005.09.001}, 2006.
Jarvis, J. C., Hastings, M. G., Steig, E. J., Kunasek, S. A.: Isotopic ratios in gas-phase HNO3 and snow nitrate at Summit, Greenland, J. Geophys. Res., 114, D17301, https://doi.org/{10.1029/2009JD012134}, 2009.
Kaiser, J., Hastings, M. G., Houlton, B. Z., R{ö}ckmann, T., and Sigman, D. M.: Triple Oxygen Isotope Analysis of Nitrate Using the Denitrifier Method and Thermal Decomposition of N}2{O, Anal. Chem., 79, 599–607, https://doi.org/{10.1021/ac061022s}, 2007.
Kunasek, S. A., Alexander, B., Steig, E. J., Hastings, M. G., Gleason, D. J., and Jarvis, J. C.: Measurements and modeling of Δ17{O} of nitrate in snowpits from S}ummit, {G}reenland, J. Geophys. Res., 113, D24302, https://doi.org/{10.1029/2008JD010103, 2008.
Legrand, M. R. and Delmas, R. J.: Soluble impurities in four {A}ntarctic ice cores over the last 30 000 years, Ann. Glaciol., 10, 116–120, 1988.
Legrand, M. R., Wolff, E. W., and Wagenbach, D.: Antarctic aerosol and snow fall chemistry: Implications for deep Antarctic ice core chemistry, Ann. Glaciol., 29, 66–72, 1999.
Li, W. J., Ni, B. L., Jin, D. Q., and Zhang, Q. G.: Measurement of the absolute abundance of oxygen-17 in V}-{SMOW, Kexue Tongbao – Chinese Sci. Bull., 33, 1610–1613, 1988.
Madronich, S. and Flocke, S.: The role of solar radiation in atmospheric chemistry, in: Handbook of {E}nvironmental {C}hemistry, edited by: Boule, P., Springer Verlag, Heidelberg, 1–26, 1998.
Mariotti, A.: Atmospheric nitrogen is a reliable standard for natural 15{N} abundance measurements, Nature, 303, 685–687, 1983.
Masson-Delmotte, V., Hou, S., Ekaykin, A., Jouzel, J., Aristarain, A., Bernardo, R. T., Bromwich, D., Cattani, O., Delmotte, M., Falourd, S., Frezzotti, M., Gallee, H., Genoni, L., Isaksson, E., Landais, A., Helsen, M. M., Hoffmann, G., Lopez, J., Morgan, V., Motoyama, H., Noone, D., Oerter, H., Petit, J. R., Royer, A., Uemura, R., Schmidt, G. A., Schlosser, E., Simoes, J. C., Steig, E. J., Stenni, B., Stievenard, M., van den Broeke, M. R., de Wal, R. S. W. V., de Berg, W. J. V., Vimeux, F., and White, J. W. C.: A review of Antarctic surface snow isotopic composition: Observations, atmospheric circulation, and isotopic modeling, J. Climate, 21, 3359–3387, https://doi.org/{10.1175/2007JCLI2139.1}, 2008.
McCabe, J. R., Boxe, C. S., Colussi, A. J., Hoffmann, M. R., and Thiemens, M. H.: Oxygen isotopic fractionation in the photochemistry of nitrate in water and ice, J. Geophys. Res., 110, D15310, https://doi.org/{10.1029/2004JD005484}, 2005.
McCabe, J. R., Thiemens, M. H., and Savarino, J.: A record of ozone variability in S}outh {P}ole {A}ntarctic snow: Role of nitrate oxygen isotopes, J. Geophys. Res., 112, D12303, https://doi.org/{10.1029/2006JD007822, 2007.
Meijer, H. A. J. and Li, W. J.: The use of electrolysis for accurate delta O-17 and delta O-18 isotope measurements in water, Isot. Environ. Healt. S., 34, 349–369, 1998.
Miller, C. E. and Yung, Y. L.: Photo-induced isotopic fractionation, J. Geophys. Res., 105(D23), 29039–29051, 2000.
Monse, E. U., Spindel, W., and Stern, M. J.: Analysis of isotope effect calculations illustrated with exchange equilibria among oxynitrogen compounds, in: ACS Advances in Chemistry, 89, 148–184, 1969.
Morin, S., Savarino, J., Bekki, S., Gong, S., and Bottenheim, J. W.: Signature of Arctic surface ozone depletion events in the isotope anomaly (${\Delta}^{17}$O) of atmospheric nitrate, Atmos. Chem. Phys., 7, 1451–1469, 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 A}tlantic Ocean boundary layer from 65 S to 79 N, J. Geophys. Res., 114, D05303, https://doi.org/{10.1029/2008JD010696, 2009.
Mulvaney, R. and Wolff, E. W.: {E}vidence for {W}inter {S}pring {D}enitrification of the {S}tratosphere in the {N}itrate {R}ecord of {A}ntarctic {F}irn {C}ores, J. Geophys. Res., 98(D3), 5213–5220, 1993.
Mulvaney, R., Wagenbach, D., and Wolff, E. W.: Postdepositional change in snowpack nitrate from observation of year-round near-surface snow in coastal {A}ntarctica, J. Geophys. Res., 103, 11021–11031, 1998.
Oi, T.: Vapor pressure isotope effects of water studied by molecular orbital calculations, J. Nucl. Sci. Technol., 40(7), 517–523, 2003.
Pettre, P., Pinglot, J. F., Pourchet, M., and Reynaud, L.: Accumulation distribution in {T}erre {A}delie, {A}ntarctica – {E}ffect of meteorological parameters, J. Glaciol., 32, 486–500, 1986.
Pursell, C. J., Everest, M. A., Falgout, M. E., and Sanchez, D. D.: Ionization of nitric acid on ice, J. Phys. Chem. A, 106, 7764–7768, https://doi.org/{10.1021/jp025697k}, 2002.
R{ö}thlisberger, R., Hutterli, M. A., Sommer, S., Wolff, E. W., and Mulvaney, R.: Factors controlling nitrate in ice cores: Evidence from the Dome C deep ice core, J. Geophys. Res., 105, 20565–20572, 2000.
R{ö}thlisberger, R., Hutterli, M. A., Wolff, E. W., Mulvaney, R., Fischer, H., Bigler, M., Goto-Azuma, K., Hansson, M. E., Ruth, U., Siggaard-Andersen, M. L., and Steffensen, J. P.: Nitrate in {G}reenland and {A}ntarctic ice cores: a detailed description of post-depositional processes, Ann. Glaciol., 35, 209–216, 2002.
Sato, K., Takenaka, N., Bandow, H., and Maeda, Y.: Evaporation loss of dissolved volatile substances from ice surfaces, J. Phys. Chem. A, 112, 7600–7607, 2008.
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, 2007.
Sigman, D. M., Casciotti, K. L., Andreani, M., Barford, C., Galanter, M., and Bohlke, J. K.: A bacterial method for the nitrogen isotopic analysis of nitrate in seawater and freshwater, Anal. Chem., 73, 4145–4153, 2001.
Silva, S. R., Kendall, C., Wilkison, D. H., Ziegler, A. C., Chang, C. C. Y., and Avanzino, R. J.: A new method for collection of nitrate from fresh water and the analysis of nitrogen and oxygen isotope ratios, J. Hydrol., 228, 22–36, 2000.
Taylor, J. R.: An Introduction to Error Analysis: The study of uncertainties in physical measurements, University Science Books, 2nd edition, 1997.
Thibert, E. and Domine, F.: Thermodynamics and kinetics of the solid solution of HNO3 in ice, J. Phys. Chem. B, 102, 4432–4439, 1998.
Thomas, J. L., Roeselova, M., Dang, L. X., and Tobias, D. J.: Molecular dynamics simulations of the solution-air interface of aqueous sodium nitrate, J. Phys. Chem. A, 111, 3091–3098, https://doi.org/{10.1021/jpl0683972}, 2007.
Traversi, R., Becagli, S., Castellano, E., Cerri, O., Morganti, A., Severi, M., and Udisti, R.: Study of Dome C site (East Antarctica) variability by comparing chemical stratigraphies, Microchem. J., 92(1), 7–14, https://doi.org/{10.1016/j.microc.2008.08.007}, 2009.
Urey, H. C.: The thermodynamic properties of isotopic substances, J. Chem. Soc., 562–581, 1947.
Wagenbach, D., Legrand, M., Fischer, H., Pichlmayer, F., and Wolff, E. W.: Atmospheric near-surface nitrate at coastal Antarctic sites, J. Geophys. Res., 103, 11007–11020, 1998.
Wang, S. Z., Bianco, R., and Hynes, J. T.: Depth-dependent dissociation of nitric acid at an aqueous surface: C}ar-{P}arrinello molecular dynamics, J. Phys. Chem. A, 113, 1295–1307, https://doi.org/{10.1021/jp808533y, 2009.
Wolff, E. W. and Delmas, R. J.: Nitrate in Polar Ice, in: Ice Core Studies of Global Biogeochemical Cycles, edited by: Delmas, R. J., Springer Verlag, NATO ASI Series I, 30, 195–224, 1995.
Wolff, E. W., Jones, A. E., Martin, T. J., and Grenfell, T. C.: Modelling photochemical NO}x production and nitrate loss in the upper snowpack of {A}ntarctica, Geophys. Res. Lett., 29(20), 1944, https://doi.org/{10.1029/2002GL015823, 2002.
Wolff, E. W., Jones, A. E., Bauguitte, S. J.-B., and Salmon, R. A.: The interpretation of spikes and trends in concentration of nitrate in polar ice cores, based on evidence from snow and atmospheric measurements, Atmos. Chem. Phys., 8, 5627–5634, 2008.
Yung, Y. L. and Miller, C. E.: Isotopic fractionation of stratospheric nitrous oxide, Science, 278, 1778–1780, 1997.
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