Articles | Volume 22, issue 2
https://doi.org/10.5194/acp-22-1081-2022
© Author(s) 2022. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/acp-22-1081-2022
© Author(s) 2022. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
The importance of alkyl nitrates and sea ice emissions to atmospheric NOx sources and cycling in the summertime Southern Ocean marine boundary layer
Jessica M. Burger
CORRESPONDING AUTHOR
Department of Oceanography, University of Cape Town, Rondebosch, 7701, South Africa
Julie Granger
Department of Marine Sciences, University of Connecticut, Groton, CT 06340, USA
Emily Joyce
Department of Earth, Environmental and Planetary Sciences and
Institute at Brown for Environment and Society, Brown University,
Providence, RI 02906, USA
Meredith G. Hastings
Department of Earth, Environmental and Planetary Sciences and
Institute at Brown for Environment and Society, Brown University,
Providence, RI 02906, USA
Kurt A. M. Spence
Department of Oceanography, University of Cape Town, Rondebosch, 7701, South Africa
Katye E. Altieri
Department of Oceanography, University of Cape Town, Rondebosch, 7701, South Africa
Related authors
Jessica M. Burger, Emily Joyce, Meredith G. Hastings, Kurt A. M. Spence, and Katye E. Altieri
Atmos. Chem. Phys., 23, 5605–5622, https://doi.org/10.5194/acp-23-5605-2023, https://doi.org/10.5194/acp-23-5605-2023, 2023
Short summary
Short summary
A seasonal analysis of the nitrogen isotopes of atmospheric nitrate over the remote Southern Ocean reveals that similar natural NOx sources dominate in spring and summer, while winter is representative of background-level conditions. The oxygen isotopes suggest that similar oxidation pathways involving more ozone occur in spring and winter, while the hydroxyl radical is the main oxidant in summer. This work helps to constrain NOx cycling and oxidant budgets in a data-sparse remote marine region.
Mhlangabezi Mdutyana, Tanya Marshall, Xin Sun, Jessica M. Burger, Sandy J. Thomalla, Bess B. Ward, and Sarah E. Fawcett
Biogeosciences, 19, 3425–3444, https://doi.org/10.5194/bg-19-3425-2022, https://doi.org/10.5194/bg-19-3425-2022, 2022
Short summary
Short summary
Nitrite-oxidizing bacteria in the winter Southern Ocean show a high affinity for nitrite but require a minimum (i.e., "threshold") concentration before they increase their rates of nitrite oxidation significantly. The classic Michaelis–Menten model thus cannot be used to derive the kinetic parameters, so a modified equation was employed that also yields the threshold nitrite concentration. Dissolved iron availability may play an important role in limiting nitrite oxidation.
Shantelle Smith, Katye E. Altieri, Mhlangabezi Mdutyana, David R. Walker, Ruan G. Parrott, Sedick Gallie, Kurt A. M. Spence, Jessica M. Burger, and Sarah E. Fawcett
Biogeosciences, 19, 715–741, https://doi.org/10.5194/bg-19-715-2022, https://doi.org/10.5194/bg-19-715-2022, 2022
Short summary
Short summary
Ammonium is a crucial yet poorly understood component of the Southern Ocean nitrogen cycle. We attribute our finding of consistently high ammonium concentrations in the winter mixed layer to limited ammonium consumption and sustained ammonium production, conditions under which the Southern Ocean becomes a source of carbon dioxide to the atmosphere. From similar data collected over an annual cycle, we propose a seasonal cycle for ammonium in shallow polar waters – a first for the Southern Ocean.
Wendell W. Walters, Masayuki Takeuchi, Danielle E. Blum, Gamze Eris, David Tanner, Weiqi Xu, Jean Rivera-Rios, Fobang Liu, Tianchang Xu, Greg Huey, Justin B. Min, Rodney Weber, Nga L. Ng, and Meredith G. Hastings
Atmos. Chem. Phys., 25, 10707–10730, https://doi.org/10.5194/acp-25-10707-2025, https://doi.org/10.5194/acp-25-10707-2025, 2025
Short summary
Short summary
We studied how chemicals released from plants and pollution interact in the atmosphere, affecting air quality and climate. By combining laboratory experiments and chemistry models, we tracked unique chemical fingerprints to understand how nitrogen compounds transform to form particles in the air. Our findings help explain the role of these reactions in pollution and provide tools to improve predictions for cleaner air and better climate policies.
Wendell W. Walters, Masayuki Takeuchi, Nga L. Ng, and Meredith G. Hastings
Geosci. Model Dev., 17, 4673–4687, https://doi.org/10.5194/gmd-17-4673-2024, https://doi.org/10.5194/gmd-17-4673-2024, 2024
Short summary
Short summary
The study introduces a novel chemical mechanism for explicitly tracking oxygen isotope transfer in oxidized reactive nitrogen and odd oxygen using the Regional Atmospheric Chemistry Mechanism, version 2. This model enhances our ability to simulate and compare oxygen isotope compositions of reactive nitrogen, revealing insights into oxidation chemistry. The approach shows promise for improving atmospheric chemistry models and tropospheric oxidation capacity predictions.
Rebecca M. Garland, Katye E. Altieri, Laura Dawidowski, Laura Gallardo, Aderiana Mbandi, Nestor Y. Rojas, and N'datchoh E. Touré
Atmos. Chem. Phys., 24, 5757–5764, https://doi.org/10.5194/acp-24-5757-2024, https://doi.org/10.5194/acp-24-5757-2024, 2024
Short summary
Short summary
This opinion piece focuses on two geographical areas in the Global South where the authors are based that are underrepresented in atmospheric science. This opinion provides context on common challenges and constraints, with suggestions on how the community can address these. The focus is on the strengths of atmospheric science research in these regions. It is these strengths, we believe, that highlight the critical role of Global South researchers in the future of atmospheric science research.
Josie L. Mottram, Anne M. Gothmann, Maria G. Prokopenko, Austin Cordova, Veronica Rollinson, Katie Dobkowski, and Julie Granger
Biogeosciences, 21, 1071–1091, https://doi.org/10.5194/bg-21-1071-2024, https://doi.org/10.5194/bg-21-1071-2024, 2024
Short summary
Short summary
Knowledge of ancient ocean N cycling can help illuminate past climate change. Using field and lab studies, this work ground-truths a promising proxy for marine N cycling, the N isotope composition of cold-water coral (CWC) skeletons. Our results estimate N turnover in CWC tissue; quantify the isotope effects between CWC tissue, diet, and skeleton; and suggest that CWCs possibly feed mainly on metazoan zooplankton, suggesting that the marine N proxy may be sensitive to the food web structure.
Jessica M. Burger, Emily Joyce, Meredith G. Hastings, Kurt A. M. Spence, and Katye E. Altieri
Atmos. Chem. Phys., 23, 5605–5622, https://doi.org/10.5194/acp-23-5605-2023, https://doi.org/10.5194/acp-23-5605-2023, 2023
Short summary
Short summary
A seasonal analysis of the nitrogen isotopes of atmospheric nitrate over the remote Southern Ocean reveals that similar natural NOx sources dominate in spring and summer, while winter is representative of background-level conditions. The oxygen isotopes suggest that similar oxidation pathways involving more ozone occur in spring and winter, while the hydroxyl radical is the main oxidant in summer. This work helps to constrain NOx cycling and oxidant budgets in a data-sparse remote marine region.
Claire Bekker, Wendell W. Walters, Lee T. Murray, and Meredith G. Hastings
Atmos. Chem. Phys., 23, 4185–4201, https://doi.org/10.5194/acp-23-4185-2023, https://doi.org/10.5194/acp-23-4185-2023, 2023
Short summary
Short summary
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.
Heejeong Kim, Wendell W. Walters, Claire Bekker, Lee T. Murray, and Meredith G. Hastings
Atmos. Chem. Phys., 23, 4203–4219, https://doi.org/10.5194/acp-23-4203-2023, https://doi.org/10.5194/acp-23-4203-2023, 2023
Short summary
Short summary
Atmospheric nitrate has an important impact on human and ecosystem health. We evaluated atmospheric nitrate formation pathways in the northeastern US utilizing oxygen isotope compositions, which indicated a significant difference between the phases of nitrate (i.e., gas vs. particle). Comparing the observations with model simulations indicated that N2O5 hydrolysis chemistry was overpredicted. Our study has important implications for improving atmospheric chemistry model representation.
Wendell W. Walters, Madeline Karod, Emma Willcocks, Bok H. Baek, Danielle E. Blum, and Meredith G. Hastings
Atmos. Chem. Phys., 22, 13431–13448, https://doi.org/10.5194/acp-22-13431-2022, https://doi.org/10.5194/acp-22-13431-2022, 2022
Short summary
Short summary
Atmospheric ammonia and its products are a significant source of urban haze and nitrogen deposition. We have investigated the seasonal source contributions to a mid-sized city in the northeastern US megalopolis utilizing geospatial statistical analysis and novel isotopic constraints, which indicate that vehicle emissions were significant components of the urban-reduced nitrogen budget. Reducing vehicle ammonia emissions should be considered to improve ecosystems and human health.
Mhlangabezi Mdutyana, Tanya Marshall, Xin Sun, Jessica M. Burger, Sandy J. Thomalla, Bess B. Ward, and Sarah E. Fawcett
Biogeosciences, 19, 3425–3444, https://doi.org/10.5194/bg-19-3425-2022, https://doi.org/10.5194/bg-19-3425-2022, 2022
Short summary
Short summary
Nitrite-oxidizing bacteria in the winter Southern Ocean show a high affinity for nitrite but require a minimum (i.e., "threshold") concentration before they increase their rates of nitrite oxidation significantly. The classic Michaelis–Menten model thus cannot be used to derive the kinetic parameters, so a modified equation was employed that also yields the threshold nitrite concentration. Dissolved iron availability may play an important role in limiting nitrite oxidation.
Shantelle Smith, Katye E. Altieri, Mhlangabezi Mdutyana, David R. Walker, Ruan G. Parrott, Sedick Gallie, Kurt A. M. Spence, Jessica M. Burger, and Sarah E. Fawcett
Biogeosciences, 19, 715–741, https://doi.org/10.5194/bg-19-715-2022, https://doi.org/10.5194/bg-19-715-2022, 2022
Short summary
Short summary
Ammonium is a crucial yet poorly understood component of the Southern Ocean nitrogen cycle. We attribute our finding of consistently high ammonium concentrations in the winter mixed layer to limited ammonium consumption and sustained ammonium production, conditions under which the Southern Ocean becomes a source of carbon dioxide to the atmosphere. From similar data collected over an annual cycle, we propose a seasonal cycle for ammonium in shallow polar waters – a first for the Southern Ocean.
Raquel F. Flynn, Thomas G. Bornman, Jessica M. Burger, Shantelle Smith, Kurt A. M. Spence, and Sarah E. Fawcett
Biogeosciences, 18, 6031–6059, https://doi.org/10.5194/bg-18-6031-2021, https://doi.org/10.5194/bg-18-6031-2021, 2021
Short summary
Short summary
Biological activity in the shallow Weddell Sea affects the biogeochemistry of recently formed deep waters. To investigate the drivers of carbon and nutrient export, we measured rates of primary production and nitrogen uptake, characterized the phytoplankton community, and estimated nutrient depletion ratios across the under-sampled western Weddell Sea in mid-summer. Carbon export was highest at the ice shelves and was determined by a combination of physical, chemical, and biological factors.
Jiajue Chai, Jack E. Dibb, Bruce E. Anderson, Claire Bekker, Danielle E. Blum, Eric Heim, Carolyn E. Jordan, Emily E. Joyce, Jackson H. Kaspari, Hannah Munro, Wendell W. Walters, and Meredith G. Hastings
Atmos. Chem. Phys., 21, 13077–13098, https://doi.org/10.5194/acp-21-13077-2021, https://doi.org/10.5194/acp-21-13077-2021, 2021
Short summary
Short summary
Nitrous acid (HONO) derived from wildfire emissions plays a key role in controlling atmospheric oxidation chemistry. However, the HONO budget remains poorly constrained. By combining the field-observed concentrations and novel isotopic composition (N and O) of HONO and nitrogen oxides (NOx), we quantitatively constrained the relative contribution of each pathway to secondary HONO production and the relative importance of major atmospheric oxidants (ozone versus peroxy) in aged wildfire smoke.
Veronica R. Rollinson, Julie Granger, Sydney C. Clark, Mackenzie L. Blanusa, Claudia P. Koerting, Jamie M. P. Vaudrey, Lija A. Treibergs, Holly C. Westbrook, Catherine M. Matassa, Meredith G. Hastings, and Craig R. Tobias
Biogeosciences, 18, 3421–3444, https://doi.org/10.5194/bg-18-3421-2021, https://doi.org/10.5194/bg-18-3421-2021, 2021
Short summary
Short summary
We measured nutrients and the naturally occurring nitrogen (N) and oxygen (O) stable isotope ratios of nitrate discharged from a New England river over an annual cycle, to monitor N loading and identify dominant sources from the watershed. We uncovered a seasonality to loading and sources of N from the watershed. Seasonality in the nitrate isotope ratios also informed on N cycling, conforming to theoretical expectations of riverine nutrient cycling.
Guitao Shi, Hongmei Ma, Zhengyi Hu, Zhenlou Chen, Chunlei An, Su Jiang, Yuansheng Li, Tianming Ma, Jinhai Yu, Danhe Wang, Siyu Lu, Bo Sun, and Meredith G. Hastings
The Cryosphere, 15, 1087–1095, https://doi.org/10.5194/tc-15-1087-2021, https://doi.org/10.5194/tc-15-1087-2021, 2021
Short summary
Short summary
It is important to understand atmospheric chemistry over Antarctica under a changing climate. Thus snow collected on a traverse from the coast to Dome A was used to investigate variations in snow chemistry. The non-sea-salt fractions of K+, Mg2+, and Ca2+ are associated with terrestrial inputs, and nssCl− is from HCl. In general, proportions of non-sea-salt fractions of ions to the totals are higher in the interior areas than on the coast, and the proportions are higher in summer than in winter.
Wendell W. Walters, Linlin Song, Jiajue Chai, Yunting Fang, Nadia Colombi, and Meredith G. Hastings
Atmos. Chem. Phys., 20, 11551–11567, https://doi.org/10.5194/acp-20-11551-2020, https://doi.org/10.5194/acp-20-11551-2020, 2020
Short summary
Short summary
This article details new field observations of the nitrogen stable isotopic composition of ammonia emitted from vehicles conducted in the US and China. Vehicle emissions of ammonia may be a significant source to urban regions with important human health and environmental implications. Our measurements have indicated a consistent isotopic signature from vehicle ammonia emissions. The nitrogen isotopic composition of ammonia may be a useful tool for tracking vehicle emissions.
Cited articles
Alexander, B. and Mickley, L. J.: Paleo-perspectives on the potential
future changes in the oxidative capacity of the atmosphere due to climate
change and anthropogenic emissions, Current Pollution Reports, 1, 57–69,
https://doi.org/10.1007/s40726-015-0006-0, 2015.
Alexander, B., Sherwen, T., Holmes, C. D., Fisher, J. A., Chen, Q., Evans, M. J., and Kasibhatla, P.: Global inorganic nitrate production mechanisms: comparison of a global model with nitrate isotope observations, Atmos. Chem. Phys., 20, 3859–3877, https://doi.org/10.5194/acp-20-3859-2020, 2020.
Altieri, K. E., Hastings, M. G., Gobel, A. R., Peters, A. J., and Sigman, D.
M.: Isotopic composition of rainwater nitrate at Bermuda: the influence of
air mass source and chemistry in the marine boundary layer, J. Geophys. Res.-Atmos., 118, 11304–11316, https://doi.org/10.1002/jgrd.50829, 2013.
Altieri, K. E., Fawcett, S. E., Peters, A. J., Sigman, D. M., and Hastings,
M. G.: Marine biogenic source of atmospheric organic nitrogen in the
subtropical North Atlantic, P. Natl. Acad. Sci. USA, 113, 925–930,
https://doi.org/10.1073/pnas.1516847113, 2016.
Altieri, K. E., Fawcett, S. E., and Hastings, M. G.: Reactive Nitrogen
Cycling in the Atmosphere and Ocean, Annu. Rev. Earth Pl. Sc., 49, 513–540, https://doi.org/10.1146/annurev-earth-083120-052147, 2021.
Atlas, E., Pollock, W., Greenberg, J., Heidt, L., and Thompson, A. M..:
Alkyl nitrates, nonmethane hydrocarbons, and halocarbon gases over the
equatorial Pacific Ocean during Saga 3, J. Geophys. Res., 98, 16933–16947, https://doi.org/10.1029/93JD01005, 1993.
Baker, A. R., Lesworth, T., Adams, C., Jickells, T. D., and Granzeveld, L.:
Estimation of atmospheric nutrient inputs to the Atlantic Ocean from
50∘ N to 50∘ S based on large-scale field sampling: Fixed nitrogen and dry deposition of phosphorus, Global Biogeochem. Cy., 24, GB3006, https://doi.org/10.1029/2009GB003634, 2010.
Bauguitte, S. J.-B., Bloss, W. J., Evans, M. J., Salmon, R. A., Anderson, P. S., Jones, A. E., Lee, J. D., Saiz-Lopez, A., Roscoe, H. K., Wolff, E. W., and Plane, J. M. C.: Summertime NOx measurements during the CHABLIS campaign: can source and sink estimates unravel observed diurnal cycles?, Atmos. Chem. Phys., 12, 989–1002, https://doi.org/10.5194/acp-12-989-2012, 2012.
Berhanu, T. A., Meusinger, C., Erbland, J., Jost, R., Bhattacharya, S. K.,
Johnson, M. S., and Savarino, J.: Laboratory study of nitrate photolysis in
Antarctic snow. II. Isotopic effects and wavelength dependence, J. Chem.
Phys., 140, 244306, https://doi.org/10.1063/1.4882899, 2014.
Berhanu, T. A., Savarino, J., Erbland, J., Vicars, W. C., Preunkert, S., Martins, J. F., and Johnson, M. S.: Isotopic effects of nitrate photochemistry in snow: a field study at Dome C, Antarctica, Atmos. Chem. Phys., 15, 11243–11256, https://doi.org/10.5194/acp-15-11243-2015, 2015.
Blake, N. J., Blake, D. R., Wingenter, O. W., Sive, B. C., Kang, C. H.,
Thornton, D. C., Bandy, A. R., Atlas, E., Flocke, F., Harris, J. M., and
Rowland, F. S.: Aircraft measurements of the latitudinal, vertical, and
seasonal variations of NMHCs, methyl nitrate, methyl halides, and DMS during
the First Aerosol Characterization Experiment (ACE 1), J. Geophys. Res., 104, 21803–21817, https://doi.org/10.1029/1999JD900238, 1999.
Blake, N. J., Blake, D. R., Swanson, A. L., Atlas, E., Flocke, F., and
Rowland, F. S.: Latitudinal, vertical, and seasonal variations of
C1-C4 alkyl nitrate in the troposphere over the Pacific Ocean
during PEM-Tropics A and B: Oceanic and continental sources, J. Geophys. Res., 108, 8242, https://doi.org/10.1029/2001JD001444, 2003.
Bölhke, J. K., Mroczkowski, S. J., and Coplen, T. B.: Oxygen isotopes in
nitrate: new reference materials for 18O:17O:16O measurements
and observations on nitrate-water equilibrium, Rapid Commun. Mass Sp., 17, 1835–1846, https://doi.org/10.1002/rcm.1123, 2003.
Brough, N., Jones, A. E., and Griffiths, P. T.: Influence of sea ice-derived
halogens on atmospheric HOx as observed in Springtime coastal
Antarctica, Geophys. Res. Lett., 46, 10168–10176, https://doi.org/10.1029/2019GL083825, 2019.
Burger, J. M., Granger, J., Joyce, E., Hastings, M. G., Spence, K. A. M., and Altieri, K. E.: The importance of alkyl nitrates and sea ice emissions to atmospheric NOx sources and cycling in the summertime Southern Ocean marine boundary layer, Version 3, Zenodo [data set], https://doi.org/10.5281/zenodo.5840260, 2021.
Casciotti, K. L., Sigman, D. M., Hastings, M. G., 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, https://doi.org/10.1021/ac020113w, 2002.
Chuck, A. L., Turner, S. M., and Liss, P. S.: Direct evidence for a marine
source of C1 and C2 alkyl nitrates, Science, 297, 1151–1154,
https://doi.org/10.1126/science.1073896, 2002.
Collett, K. S., Piketh, S. J., and Ross, K. E.: An assessment of the
atmospheric nitrogen budget on the South African Highveld, S. Afr. J. Sci.,
106, 1–9, https://doi.org/10.4102/sajs.v106i5/6.220, 2010.
Dahl, E. E. and Saltzman, S. E.: Alkyl nitrate photochemical production
rates in North Pacific seawater, Mar. Chem., 112, 137–141,
https://doi.org/10.1016/j.marchem.2008.10.002, 2008.
Dahl, E. E., Saltzman, S. E., and de Bruyn, W. J.: The aqueous phase yield
of alkyl nitrates from ROO + NO: Implications for photochemical production
in seawater, Geophys. Res. Lett., 30, 1271, https://doi.org/10.1029/2002GL016811, 2003.
Dahl, E. E., Yvon-Lewis, S. A., and Saltzman, S. E.: Saturation anomalies of
alkyl nitrates in the tropical Pacific Ocean, Geophys. Res. Lett.,
32, L20817, https://doi.org/10.1029/2005GL023896, 2005.
Dahl, E. E., Heiss, E. M., and Murawski, K.: The effects of dissolved
organic matter on alkyl nitrate production during GOMECC and laboratory
studies, Mar. Chem., 142, 11–17, https://doi.org/10.1016/j.marchem.2012.08.001, 2012.
Dar, S. S., Ghosh, P., Swaraj, A., and Kumar, A.: Craig–Gordon model validation using stable isotope ratios in water vapor over the Southern Ocean, Atmos. Chem. Phys., 20, 11435–11449, https://doi.org/10.5194/acp-20-11435-2020, 2020.
Davidson, E. A. and Kingerlee, W.: A global inventory of nitric oxide
emissions from soils, Nutr. Cycl. Agroecosys., 48, 37–50,
https://doi.org/10.1023/A:1009738715891, 1997.
Elliott, E. M., Kendall, C., Wankel, S. D., Burns, S. A., Boyer, E. W.,
Harlin, K., Bain, D. J., and Butler, T. J.: Nitrogen isotopes as indicators
of NOx source contributions to atmospheric nitrate deposition across the Midwestern and Northeastern United States, Environ. Sci. Technol., 41, 7661–7667, https://doi.org/10.1021/es070898t, 2007.
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.
Fang, Y. T., Koba, K., Wang, X. M., Wen, D. Z., Li, J., Takebayashi, Y., Liu, X. Y., and Yoh, M.: Anthropogenic imprints on nitrogen and oxygen isotopic composition of precipitation nitrate in a nitrogen-polluted city in southern China, Atmos. Chem. Phys., 11, 1313–1325, https://doi.org/10.5194/acp-11-1313-2011, 2011.
Finlayson-Pitts, B. J. and Pitts, J. N.: Chemistry of the upper and lower
troposphere, Academic Press, San Diego, California, https://doi.org/10.1016/B978-0-12-257060-5.X5000-X, 2000.
Fisher, J. A., Atlas, E. L., Barletta, B., Meinardi, S., Blake, D. R.,
Thompson, C. R., Ryerson, T. B., Peischl, J., Tzompa-Sosa, Z. A., and
Murray, L. T.: Methyl, ethyl and propyl nitrates: global distribution and
impacts on reactive nitrogen in remote marine environments, J. Geophys. Res.-Atmos., 123, 12412–12429, https://doi.org/10.1029/2018JD029046, 2018.
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.
Freyer, H. D., Kley, D., Volz-Thomas, A., and Kobel, K.: On the interaction
of isotopic exchange processes with photochemical reactions in atmospheric
oxides of nitrogen, J. Geophys. Res., 98, 14791–14796,
https://doi.org/10.1029/93JD00874, 1993.
Freyer, H. D., Kobel, K., Delmas, R. J., Kley, D., and Legrand, M. R.: First
results of ratios in nitrate from alpine and polar ice
cores, Tellus B, 48, 93–105, https://doi.org/10.3402/tellusb.v48i1.15671, 1996.
Gobel, A. R., Altieri, K. E., Peters, A. J., Hastings, M. G., and Sigman, D.
M.: Insights into anthropogenic nitrogen deposition to the North Atlantic
investigated using the isotopic composition of aerosol and rainwater
nitrate, Geophys. Res. Lett., 40, 5977–5982,
https://doi.org/10.1002/2013GL058167, 2013.
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, https://doi.org/10.5194/acp-7-4329-2007, 2007.
Grasshoff, K., Kremling, K., and Ehrhardt, M.: Methods of seawater
analysis, Verlag Chemi, Florida, 1983.
Guilpart, E., Vimeux, F., Evan, S., Brioude, J., Mertzger, J., Barthe, C.,
Risi, C., and Cattani, O.: The isotopic composition of near-surface water
vapor at the Maïdo observatory (Reunion Island, southwestern Indian
Ocean) documents the controls of the humidity of the subtropical
troposphere, J. Geophys. Res.-Atmos., 122, 9628–9650,
https://doi.org/10.1002/2017JD026791, 2017.
Hamilton, D. S., Lee, L. A., Pringle, K. J., Reddington, C. L., Spracklen,
D. V., and Carslaw, K. S.: Occurence of pristine aerosol environments on a
polluted planet, P. Natl. Acad. Sci. USA, 111, 18466–18471,
https://doi.org/10.1073/pnas.1415440111, 2014.
Hastings, M. G., Sigman, D. M., and Lipschultz, F.: Isotopic evidence for
source changes of nitrate in rain at Bermuda, J. Geophys. Res., 108, 4790, https://doi.org/10.1029/2003JD003789, 2003.
Haywood, J. and Boucher, O.: Estimates of the direct and indirect radiative
forcing due to tropospheric aerosols: a review, Rev. Geophys., 38, 513–543,
https://doi.org/10.1029/1999RG000078, 2000.
Hoering, T.: The isotopic composition of the ammonia and the nitrate ion in
rain, Geochim. Cosmochim. Ac., 12, 97–102, https://doi.org/10.1016/0016-7037(57)90021-2, 1957.
Hughes, C., Chuck, A. L., Turner, S. M., and Liss, P. S.: Methyl and ethyl nitrate saturation anomalies in the Southern Ocean (36–65∘ S, 30–70∘ W), Environ. Chem., 5, 11–15, https://doi.org/10.1071/EN07083, 2008.
IPCC: Boucher, O. D., Randall, P., Artaxo, C., Bretherton, G.,
Feingold, P., Forster, V.-M., Kerminen, Y., Kondo, H., Liao, U., Lohmann,
P., Rasch, S.K., Satheesh, S., Sherwood, B., Stevens, and Zhang, X. Y.:
Clouds and Aerosols, in: Climate Change 2013: The Physical Science Basis.
Contribution of Working Group I to the Fifth Assessment Report of the
Intergovernmental Panel on Climate Change, edited by: Stocker, T. F., Qin,
D., Plattner, G.-K., Tignor, M., Allen, S. K., Boschung, J, Nauels, A., Xia,
Y., Bex, V., and Midgley, P. M., Cambridge University Press, Cambridge,
United Kingdom and New York, NY, USA, 2013.
Ishino, S., Hattori, S., Savarino, J., Jourdain, B., Preunkert, S., Legrand, M., Caillon, N., Barbero, A., Kuribayashi, K., and Yoshida, N.: Seasonal variations of triple oxygen isotopic compositions of atmospheric sulfate, nitrate, and ozone at Dumont d'Urville, coastal Antarctica, Atmos. Chem. Phys., 17, 3713–3727, https://doi.org/10.5194/acp-17-3713-2017, 2017.
Jiang, S., Shi, G., Cole-Dai, J., Geng, L., Ferris, D. G., An, C., and Li,
Y.: Nitrate preservation in snow at Dome A, East Antarctica from ice core
concentration and isotope records, Atmos. Environ., 213, 405–412,
https://doi.org/10.1016/j.atmosenv.2019.06.031, 2019.
Jones, A. E., Weller, R., Minikin, A., Wolff, E. W., Sturges, W. T.,
McIntyre, H. P., Leonard, S. R., Schrems, O., and Bauguitte, S.: Oxidized
nitrogen chemistry and speciation in the Antarctic troposphere, J. Geophys.
Res., 104, 21355–21366, https://doi.org/10.1029/1999JD900362, 1999.
Jones, A. E., Weller, R., Wolff, E. W., and Jacobi, H.-W.: Speciation and
rate of photochemical NO and NO2 production in Antarctic snow,
Geophys. Res. Lett., 27, 345–348, https://doi.org/10.1029/1999GL010885, 2000.
Jones, A. E., Weller, R., Anderson, P. S., Jacobi, H.-W., Wolff, E. W.,
Schrems, O., and Miller, H.: Measurements of NOx emissions from the Antarctic snowpack, Geophys. Res. Lett., 28, 1499–1502, https://doi.org/10.1029/2000GL011956, 2001.
Kamezaki, K., Hattori, S., Iwamoto, Y., Ishino, S., Furutani, H., Miki, Y.,
Uematsu, M., Miura, K., and Yoshida, N.: Tracing the sources and formation
pathways of atmospheric particulate nitrate over the Pacific Ocean using
stable isotopes, Atmos. Environ., 209, 152–166,
https://doi.org/10.1016/j.atmosenv.2019.04.026, 2019.
Kendall, C., Elliot, E. M., and Wankel, S. D.: Tracing anthropogenic inputs
of nitrogen to ecosystems, in: Stable isotopes in ecology and environmental
science, edited by: Michener, R. and Lajtha, K., Blackwell Publishing,
Malden, Mass, 375–449, https://doi.org/10.1002/9780470691854.ch12, 2007.
Kroopnick, P. and Craig, H.: Atmospheric oxygen: isotopic composition and
solubility fractionation, Science, 175, 54–55, 1972.
Lee, H.-M., Henze, D. K., Alexander, B., and Murray, L. T.: Investigating
the sensitivity of surface-level nitrate seasonality in Antarctica to
primary sources using a global model, Atmos. Environ., 89, 757–767,
https://doi.org/10.1016/j.atmosenv.2014.03.003, 2014.
Michalski, G., Scott, Z., Kabiling, M., and Thiemens, M. H.: First
measurments and modeling of Δ17O in atmospheric nitrate,
Geophys. Res. Lett., 30, 1870, https://doi.org/10.1029/2003GL017015, 2003.
Michalski, G., Bhattacharya, S. K., and Mase, D. F.: Oxygen isotope dynamics
of atmospheric nitrate and its precursor molcules, in: Handbook of
environmental isotope geochemistry. Advances in Isotope Geochemistry, edited
by: Baskaran, M., Springer, Berlin, Heidelberg, 613–635,
https://doi.org/10.1007/978-3-642-10637-8_30, 2012.
Monks, P. S.: Gas-phase radical chemistry in the troposphere, Chem. Soc.
Rev., 34, 376–395, https://doi.org/10.1039/B307982C, 2005.
Morin, S., Savarino, J., Frey, M. M., Domine, F., Jacobi, H. W., Kaleschke,
L., and Martins, J. M.: 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.
Nadzir, M. S., Ashfold, M. J., Khan, M. F., Robinson, A. D., Bolas, C.,
Latif, M. T., Wallis, B. M., Mead, M. I., Hamid, H. H. A., Harris, N. R. P.,
Ramly, Z. T. A., Lai, G. T., Liew, J. N., Ahamed, F., Uning, R., Samah, A.
A., Maulud, K. N., Suparta, W., Zainudin, S. K., Wahab, M. I. A., Sahani,
M., Müller , M., Yeok, F. S., Rahman, N. A., Mujahid, A., Morris, K. I.,
and Sasso, N. D.: Spatial-temporal variations in surface ozone over Ushuaia
and the Antarctic region: observations from in situ measurements, satellite
data, and global models, Environ. Sci. Pollut. R., 25, 2194–2210,
https://doi.org/10.1007/s11356-017-0521-1, 2018.
Nesbitt, S. W., Zhang, R., and Orville, R. E.: Seasonal and global NOx production by lightning estimated from the Optical Transient Detector (OTD), Tellus B, 52, 1206–1215,
https://doi.org/10.3402/tellusb.v52i5.17098, 2000.
Park, S. S. and Kim, Y. J.: Source contributions to fine particulate matter
in an urban atmosphere, Chemosphere, 59, 217–226,
https://doi.org/10.1016/j.chemosphere.2004.11.001, 2005.
Park, Y., Park, K., Kim, H., Yu, S., Noh, S., Kim, M.-S, Kim, J.-Y., Ahn,
J.-Y., Seok, K.-S., and Kim, Y.-H.: Characterizing isotopic compositions of
TC-C, NO -N and NH -N in PM2.5 in South Korea: Impact of China's winter heating, Environ. Pollut., 233, 735–744,
https://doi.org/10.1016/j.envpol.2017.10.072, 2018.
Rindelaub, J. D., McAvey, K. M., and Shepson, P. B.: The photochemical
production of organic nitrates from α-pinene and loss via
acid-dependent particle phase hydrolysis, Atmos. Environ., 100, 193–201,
https://doi.org/10.1016/j.atmosenv.2014.11.010, 2015.
Rolph, G. D.: Real-time Environmental Applications and Display System (READY) Website, NOAA Air Resources Laboratory, College Park, MD, available at: https://www.ready.noaa.gov/index.php (last access: 12 January 2022), 2016.
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.
Scarchilli, C., Frezzotti, M., and Ruti, P. M.: Snow precipitation at four
ice core sites in East Antarctica: provenance, seasonality and blocking
factors, Clim. Dynam., 37, 2107–2125, https://doi.org/10.1007/s00382-010-0946-4, 2011.
Schumann, U. and Huntrieser, H.: The global lightning-induced nitrogen oxides source, Atmos. Chem. Phys., 7, 3823–3907, https://doi.org/10.5194/acp-7-3823-2007, 2007.
Shi, G., Buffen, A. M., Hastings, M. G., Li, C., Ma, H., Li, Y., Sun, B., An, C., and Jiang, S.: Investigation of post-depositional processing of nitrate in East Antarctic snow: isotopic constraints on photolytic loss, re-oxidation, and source inputs, Atmos. Chem. Phys., 15, 9435–9453, https://doi.org/10.5194/acp-15-9435-2015, 2015.
Shi, G., Buffen, A. M., Ma, H., Hu, Z., Sun, B., Li, C., Yu, J., Ma, T., An,
C., Jiang, S., Li, Y., and Hastings, M. G.: Distinguishing summertime
atmopsheric production of nitrate across the East Antarctic ice sheet,
Geochim. Cosmochim. Ac., 231, 1–14, https://doi.org/10.1016/j.gca.2018.03.025, 2018.
Shi, G., Ma, H., Zhu, Z., Hu, A., Chen, Z., Jiang, Su., An, C., Yu, J., Ma,
T., Li, Y., Sun, B., and Hastings, M. G.: Using stable isotopes to
distinguish atmospheric nitrate production and its contribution to the
surface ocean across hemispheres, Earth Planet. Sc. Lett., 564, 116914,
https://doi.org/10.1016/j.epsl.2021.116914, 2021.
Sigman, D. M., Casciotti, K. L., Andreani, M., Barford, C., Galanter, M., and
Böhlke, J. K.: A bacterial method for the nitrogen isotopic analysis of
nitrate in seawater and freshwater, Anal. Chem., 73, 4145–4153,
https://doi.org/10.1021/ac010088e, 2001.
Sinclair, K. E., Bertler, N. A. N., Trompetter, W. J., and Baisden, W. T.:
Seasonality of airmass pathways to coastal Antarctica: ramifications for
interpreting high-resolution ice core records, J. Climate, 26, 2065–2076,
https://doi.org/10.1175/JCLI-D-12-00167.1, 2013.
Spreen, G., Kaleschke, L., and Heygster, G.: Sea ice remote sensing using
AMSR-E 89-GHz channels, J. Geophys. Res., 113, C02S03,
https://doi.org/10.1029/2005JC003384, 2008.
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.
van der A, R. J., Eskes, H. J., Boersma, K. F., van Noije, T. P., Van
Roozendael, M., De Smedt, I., Peters, D. H. M. U., and Meijer, E. W.:
Trends, seasonal variability and dominant NOx source derived from a ten year record of NO2 measured from space, J. Geophys. Res., 113, D04302, https://doi.org/10.1029/2007JD009021, 2008.
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,
https://doi.org/10.1016/j.gca.2014.03.023, 2014.
Virkkula, A., Teinilä, K., Hillamo, R., Kerminen, V.-M., Saarikoski, S., Aurela, M., Viidanoja, J., Paatero, J., Koponen, I. K., and Kulmala, M.: Chemical composition of boundary layer aerosol over the Atlantic Ocean and at an Antarctic site, Atmos. Chem. Phys., 6, 3407–3421, https://doi.org/10.5194/acp-6-3407-2006, 2006.
Walters, W. W. and Michalski, G.: Theoretical calculation of nitorgen
isotope equilibrium exchange fractionation factors for various NOy
molecules, Geochim. Cosmochim. Ac., 164, 284–297,
https://doi.org/10.1016/j.gca.2015.05.029, 2015.
Walters, W. W. and Michalski, G.: Theoretical calculation of oxygen
equilibrium isotope fractionation factors involving various NOy
molecules, OH, and H2O and its implications for isotope variations in
atmospheric nitrate, Geochim. Cosmochim. Ac., 191, 89—101,
https://doi.org/10.1016/j.gca.2016.06.039, 2016.
Walters, W. W., Simonini, D. S., and Michalski, G.: Nitrogen isotope
exchange between NO and NO2 and its implications for δ15N
variations in tropospheric NOx and atmospheric nitrate,
Geophys. Res. Lett., 43, 440–448, https://doi.org/10.1002/2015GL066438, 2016.
Walters, W. W., Michalski, G., Bohlke, J. K., Alexander, B., Savarino, J.,
and Thiemens, M. H.: Assessing the seasonal dynamics of nitrate and sulfate
aerosols at the South Pole utilizing stable isotopes, J. Geophys. Res.-Atmos., 124, 8161–8177, https://doi.org/10.1029/2019JD030517, 2019.
Weller, R., Jones, A. E., Wille, A., Jacobi, H.-W., McIntyre, H. P.,
Sturges, W. T., Huke, M., and Wagenback, D.: Seasonality of reactive
nitrogen oxides (NOy) at Neumayer Station, Antarctica, J. Geophys. Res., 107, 4673, https://doi.org/10.1029/2002JD002495, 2002.
Williams, J. E., Le Bras, G., Kukui, A., Ziereis, H., and Brenninkmeijer, C. A. M.: The impact of the chemical production of methyl nitrate from the NO + CH3O2 reaction on the global distributions of alkyl nitrates, nitrogen oxides and tropospheric ozone: a global modelling study, Atmos. Chem. Phys., 14, 2363–2382, https://doi.org/10.5194/acp-14-2363-2014,
2014.
Zong, Z., Wang, X., Tian, C., Chen, Y., Fang, Y., Zhang, F., Li, C., Sun,
J., Li, J., and Zhang, G.: First assessment of NOx sources at a regional background site in North China using isotopic analysis linked with modeling, Environ. Sci. Technol., 51, 5923–5931,
https://doi.org/10.1021/acs.est.6b06316, 2017.
Short summary
The nitrogen (N) isotopic composition of atmospheric nitrate in the Southern Ocean (SO) marine boundary layer (MBL) reveals the importance of oceanic alkyl nitrate emissions as a source of reactive N to the atmosphere. The oxygen isotopic composition suggests peroxy radicals contribute up to 63 % to NO oxidation and that nitrate forms via the OH pathway. This work improves our understanding of reactive N sources and cycling in a remote marine region, a proxy for the pre-industrial atmosphere.
The nitrogen (N) isotopic composition of atmospheric nitrate in the Southern Ocean (SO) marine...
Altmetrics
Final-revised paper
Preprint