Articles | Volume 23, issue 10
https://doi.org/10.5194/acp-23-5605-2023
© Author(s) 2023. 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-23-5605-2023
© Author(s) 2023. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
22 May 2023
Research article |
| 22 May 2023
| 22 May 2023
A seasonal analysis of aerosol NO3− sources and NOx oxidation pathways in the Southern Ocean marine boundary layer
Jessica M. Burger
CORRESPONDING AUTHOR
Department of Oceanography, University of Cape Town, Rondebosch, 7701, South Africa
Emily Joyce
Department of Earth, Environmental and Planetary Science, Brown University, Providence, RI 02906, USA
Institute at Brown for Environment and Society, Brown University, Providence, RI 02906, USA
Meredith G. Hastings
Department of Earth, Environmental and Planetary Science, Brown University, Providence, RI 02906, USA
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
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.
Jessica M. Burger, Julie Granger, Emily Joyce, Meredith G. Hastings, Kurt A. M. Spence, and Katye E. Altieri
Atmos. Chem. Phys., 22, 1081–1096, https://doi.org/10.5194/acp-22-1081-2022, https://doi.org/10.5194/acp-22-1081-2022, 2022
Short summary
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.
Rebecca M. Garland, Katye E. Altieri, Laura Dawidowski, Laura Gallardo, Aderiana Mbandi, Nestor Y. Rojas, and N'datchoh E. Touré
EGUsphere, https://doi.org/10.5194/egusphere-2023-2566, https://doi.org/10.5194/egusphere-2023-2566, 2023
Short summary
Short summary
In this opinion, we focus on two geographical areas in the Global South to discuss some common challenges and constraints, with a focus on our strengths in atmospheric science research. It is these strengths, we believe, that highlight the critical role of Global South researchers in the future of atmospheric science research.
Wendell W. Walters, Masayuki Takeuchi, Nga L. Ng, and Meredith G. Hastings
EGUsphere, https://doi.org/10.5194/egusphere-2023-2293, https://doi.org/10.5194/egusphere-2023-2293, 2023
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.
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.
Jessica M. Burger, Julie Granger, Emily Joyce, Meredith G. Hastings, Kurt A. M. Spence, and Katye E. Altieri
Atmos. Chem. Phys., 22, 1081–1096, https://doi.org/10.5194/acp-22-1081-2022, https://doi.org/10.5194/acp-22-1081-2022, 2022
Short summary
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.
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.
Erika Marín-Spiotta, Rebecca T. Barnes, Asmeret Asefaw Berhe, Meredith G. Hastings, Allison Mattheis, Blair Schneider, and Billy M. Williams
Adv. Geosci., 53, 117–127, https://doi.org/10.5194/adgeo-53-117-2020, https://doi.org/10.5194/adgeo-53-117-2020, 2020
Short summary
Short summary
The geosciences are one of the least diverse disciplines in the United States, despite the field's relevance to people's livelihoods and economies. Bias, discrimination and harassment present serious hurdles to diversifying the field. We summarize research on the factors that contribute to the persistence of hostile climates in the geosciences and other scientific disciplines and provide recommendations for cultural change through the role of mentoring networks and professional associations.
Jiajue Chai, David J. Miller, Eric Scheuer, Jack Dibb, Vanessa Selimovic, Robert Yokelson, Kyle J. Zarzana, Steven S. Brown, Abigail R. Koss, Carsten Warneke, and Meredith Hastings
Atmos. Meas. Tech., 12, 6303–6317, https://doi.org/10.5194/amt-12-6303-2019, https://doi.org/10.5194/amt-12-6303-2019, 2019
Short summary
Short summary
Isotopic analysis offers a potential tool to distinguish between sources and interpret transformation pathways of atmospheric species. We applied recently developed techniques in our lab to characterize the isotopic composition of reactive nitrogen species (NOx, HONO, HNO3, pNO3-) in fresh biomass burning emissions. Intercomparison with other techniques confirms the suitability of our methods, allowing for future applications of our techniques in a variety of environments.
Guitao Shi, Meredith G. Hastings, Jinhai Yu, Tianming Ma, Zhengyi Hu, Chunlei An, Chuanjin Li, Hongmei Ma, Su Jiang, and Yuansheng Li
The Cryosphere, 12, 1177–1194, https://doi.org/10.5194/tc-12-1177-2018, https://doi.org/10.5194/tc-12-1177-2018, 2018
Short summary
Short summary
The deposition and preservation of NO3− across East Antarctica was investigated. On the coast, dry deposition contributes 27–44 % of the NO3− fluxes, and the linear relationship between NO3− and snow accumulation rate suggests a homogeneity of atmospheric NO3− levels. In inland snow, a relatively weak correlation between NO3− and snow accumulation was found, indicating that NO3− is mainly dominated by post-depositional processes. The coexisting ions are generally less influential on snow NO3−.
Alex R. Baker, Maria Kanakidou, Katye E. Altieri, Nikos Daskalakis, Gregory S. Okin, Stelios Myriokefalitakis, Frank Dentener, Mitsuo Uematsu, Manmohan M. Sarin, Robert A. Duce, James N. Galloway, William C. Keene, Arvind Singh, Lauren Zamora, Jean-Francois Lamarque, Shih-Chieh Hsu, Shital S. Rohekar, and Joseph M. Prospero
Atmos. Chem. Phys., 17, 8189–8210, https://doi.org/10.5194/acp-17-8189-2017, https://doi.org/10.5194/acp-17-8189-2017, 2017
Short summary
Short summary
Man's activities have greatly increased the amount of nitrogen emitted into the atmosphere. Some of this nitrogen is transported to the world's oceans, where it may affect microscopic marine plants and cause ecological problems. The huge size of the oceans makes direct monitoring of nitrogen inputs impossible, so computer models must be used to assess this issue. We find that current models reproduce observed nitrogen deposition to the oceans reasonably well and recommend future improvements.
Nathan J. Chellman, Meredith G. Hastings, and Joseph R. McConnell
The Cryosphere Discuss., https://doi.org/10.5194/tc-2016-163, https://doi.org/10.5194/tc-2016-163, 2016
Revised manuscript not accepted
Short summary
Short summary
This manuscript analyzes the changing sources of nitrate deposition to Greenland since 1760 CE using a dataset consisting of sub-seasonally resolved nitrogen isotopes of nitrate and source tracers. Correlations amongst ion concentration, source tracers, and the δ15N–NO3− provide evidence of the impact of biomass burning and fossil fuel combustion emissions of nitrogen oxides and suggest that oil combustion is the likely driver of increased nitrate concentration in Greenland ice since 1940 CE.
G. Shi, A. M. Buffen, M. G. Hastings, C. Li, H. Ma, Y. Li, B. Sun, C. An, and S. Jiang
Atmos. Chem. Phys., 15, 9435–9453, https://doi.org/10.5194/acp-15-9435-2015, https://doi.org/10.5194/acp-15-9435-2015, 2015
Short summary
Short summary
We evaluate isotopic composition of NO3- in different environments across East Antarctica. At high snow accumulation sites, isotopic ratios are suggestive of preservation of NO3- deposition. At low accumulation sites, isotopes are sensitive to both the loss of NO3- due to photolysis and secondary formation of NO3- within the snow. The imprint of post-depositional alteration is not uniform with depth, making it difficult to predict the isotopic composition at depth from near-surface data alone.
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
Related subject area
Subject: Isotopes | Research Activity: Field Measurements | Altitude Range: Troposphere | Science Focus: Chemistry (chemical composition and reactions)
Nitrate chemistry in the northeast US – Part 1: Nitrogen isotope seasonality tracks nitrate formation chemistry
Nitrate chemistry in the northeast US – Part 2: Oxygen isotopes reveal differences in particulate and gas-phase formation
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
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
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
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.
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
Short summary
Short summary
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
Short summary
Short summary
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.
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
Short summary
Short summary
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
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 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
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, 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
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.
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
Short summary
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.
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., 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., 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.
Aun, M., Lakkala, K., Sanchez, R., Asmi, E., Nollas, F., Meinander, O., Sogacheva, L., De Bock, V., Arola, A., de Leeuw, G., Aaltonen, V., Bolsée, D., Cizkova, K., Mangold, A., Metelka, L., Jakobson, E., Svendby, T., Gillotay, D., and Van Opstal, B.: Solar UV radiation measurements in Marambio, Antarctica, during years 2017–2019, Atmos. Chem. Phys., 20, 6037–6054, https://doi.org/10.5194/acp-20-6037-2020, 2020.
Baker, A. R., Weston, K., Kelly, S. D., Voss, M., Streu, P., and Cape, J. N.:
Dry and wet deposition of nutrients from the tropical Atlantic atmosphere:
links to primary productivity and nitrogen fixation, Deep Sea Res. Pt. I, 54, 1704–1720, https://doi.org/10.1016/j.dsr.2007.07.001, 2007.
Barkan, E., and Luz, B.: High precision measurements of 17O
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., Savarino, J., Bhattacharya, S. K., and Vicars, W. C.:
17O excess transfer during the NO2 + O3 → NO3 + O2 reaction, J. Chem. Phys., 136, 1–9, https://doi.org/10.1063/1.3666852, 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.
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, Atmos. Chem. Phys., 22, 1081–1096, https://doi.org/10.5194/acp-22-1081-2022, 2022a.
Burger, J. M., Joyce, E., Hastings, M. G., Spence, K. A. M., and Altieri, K. E.: A seasonal analysis of aerosol NO
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.
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., 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.
Derwent, R. G., Parrish, D. D., Galbally, I. E., Stevenson, D. S., Doherty,
R. M., Young, P. J., and Shallcross, D. E.: Interhemispheric differences in
seasonal cycles of tropospheric ozone in the marine boundary layer:
Observation-model comparisons, J. Geophys. Res.-Atmos., 121, 11075–11085,
https://doi.org/10.1002/2016JD024836, 2016.
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.
Elliot, E. M., Yu, Z., Cole, A. S., and Coughlin, J. G.: Isotopic advances
in understanding reactive nitrogen deposition and atmospheric processing,
Sci. Total Environ., 662, 393–403, https://doi.org/10.1016/j.scitotenv.2018.12.177, 2019.
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.
Fibiger, D. L., and Hastings, M. G.: First Measurements of the Nitrogen
Isotopic Composition of NOx from Biomass Burning, Environ. Sci. Technol., 50, 11569–11574, https://doi.org/10.1021/acs.est.6b03510, 2016.
Fibiger, D. L., Hastings, M. G., Dibb, J. E., and Huey, L. G.: The
preservation of atmospheric nitrate in snow at Summit, Greenland, Geophys.
Res. Lett., 40, 3484–3489, https://doi.org/10.1002/grl.50659, 2013.
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.
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.
Hamilton, D. S., Lee, L. A., Pringle, K. J., Reddington, C. L., Spracklen,
D. V., and Carslaw, K. S.: Occurrence 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.
Heidenreich, J. E. III. and Thiemens, M. H.: A non-mass-dependent oxygen
isotope effect in the production of ozone from molecular oxygen: the role of symmetry in isotope chemistry, J. Chem. Phys., 84, 2129–2136, https://doi.org/10.1063/1.450373, 1986.
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.
Hosaynali Beygi, Z., Fischer, H., Harder, H. D., Martinez, M., Sander, R., Williams, J., Brookes, D. M., Monks, P. S., and Lelieveld, J.: Oxidation photochemistry in the Southern Atlantic boundary layer: unexpected deviations of photochemical steady state, Atmos. Chem. Phys., 11, 8497–8513, https://doi.org/10.5194/acp-11-8497-2011, 2011.
IPCC: Boucher, O., Randall, D., Artaxo, P., Bretherton, C., Feingold, G., Forster, P., Kerminen, V.-M., Kondo, Y., Liao, H., Lohmann, U., Rasch, P., Satheesh, S. K., Sherwood, S., Stevens, B., 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, ISBN 9781107661820, 2013.
Ireland, T. R., Avila, J., Greenwood, R. C., Hicks, L. J., and Bridges, J.
C.: Oxygen Isotopes and Sampling of the Solar System, Space Sci. Rev.,
216, 1–60, https://doi.org/10.1007/s11214-020-0645-3, 2020.
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.
Jacobi, H.-W., Weller, R., Jones, A. E., Anderson, P. S., and Schrems, O.:
Peroxyaccetyl nitrate (PAN) concentrations in the Antarctic troposphere
measured during the photochemical experiment at Neumayer (PEAN'99), Atmos.
Environ., 34, 5235–5247, https://doi.org/10.1016/S1352-2310(00)00190-4, 2000.
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.
Jones, A. E., Wolff, E. W., Ames, D., Bauguitte, S. J.-B., Clemitshaw, K. C., Fleming, Z., Mills, G. P., Saiz-Lopez, A., Salmon, R. A., Sturges, W. T., and Worton, D. R.: The multi-seasonal NOy budget in coastal Antarctica and its link with surface snow and ice core nitrate: results from the CHABLIS campaign, Atmos. Chem. Phys., 11, 9271–9285, https://doi.org/10.5194/acp-11-9271-2011, 2011.
Joyce, E. E., Balint, S. J., and Hastings, M. G.: Isotopic evidence that
alkyl nitrates are important to aerosol nitrate formation in the equatorial
Pacific, Geophys. Res. Lett., 49, 1–10, https://doi.org/10.1029/2022GL099960, 2022.
Kaiser, J., Hastings, M. G., Houlton, B. Z., Rockmann, T., and Sigman, D.
M.: Triple Oxygen Isotope Analysis of Nitrate Using the Denitrifier Method
and Thermal Decomposition of N2O, Anal. Chem., 79, 599–607,
https://doi.org/10.1021/ac061022s, 2007.
Kaleschke, L., Richter, A., Burrows, J., Afe, O., Heygster, G., Notholt, J., Rankin, A. M., Roscoe, H. K., Hollwedel, J., Wagner, T., and Jacobi, H.-W.: Frost flowers on sea ice as a source of sea salt and their influence on tropospheric halogen chemistry, Geophys. Res. Lett., 31, L16114, https://doi.org/10.1029/2004GL020655, 2004.
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.
Kasibhatla, P., Sherwen, T., Evans, M. J., Carpenter, L. J., Reed, C., Alexander, B., Chen, Q., Sulprizio, M. P., Lee, J. D., Read, K. A., Bloss, W., Crilley, L. R., Keene, W. C., Pszenny, A. A. P., and Hodzic, A.: Global impact of nitrate photolysis in sea-salt aerosol on NOx, OH, and O3 in the marine boundary layer, Atmos. Chem. Phys., 18, 11185–11203, https://doi.org/10.5194/acp-18-11185-2018, 2018.
Lakkala, K., Aun, M., Sanchez, R., Bernhard, G., Asmi, E., Meinander, O., Nollas, F., Hülsen, G., Karppinen, T., Aaltonen, V., Arola, A., and de Leeuw, G.: New continuous total ozone, UV, VIS and PAR measurements at Marambio, 64∘ S, Antarctica, Earth Syst. Sci. Data, 12, 947–960, https://doi.org/10.5194/essd-12-947-2020, 2020.
Lawrence, M. G., and Crutzen, P. J.: Influence of NOx emissions from ships on tropospheric photochemistry and climate, Nature, 402, 167–170,
https://doi.org/10.1038/46013, 1999.
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.
Legrand, M., Preunkert, S., Frey, M., Bartels-Rausch, Th., Kukui, A., King, M. D., Savarino, J., Kerbrat, M., and Jourdain, B.: Large mixing ratios of atmospheric nitrous acid (HONO) at Concordia (East Antarctic Plateau) in summer: a strong source from surface snow?, Atmos. Chem. Phys., 14, 9963–9976, https://doi.org/10.5194/acp-14-9963-2014, 2014.
Li, J., Davy, P., Harvey, M., Katzman, T., Mitchell, T., and Michalski, G.:
Nitrogen isotopes in nitrate aerosols collected in the remote marine
boundary layer: Implications for nitrogen isotopic fractionations among
atmospheric reactive nitrogen species, Atmos. Environ., 245, 1–10,
https://doi.org/10.1016/j.atmosenv.2020.118028, 2021.
Lu, Z., Liu, X., Zaveri, R. A., Easter, R. C., Tilmes, S., Emmons, L. K., Vitt, F., Singh, B., Wang, H., Zhang, R., and Rasch, P. J.: Radiative Forcing of Nitrate Aerosols From 1975 to 2010 as Simulated by MOSAIC Module in CESM2-MAM4, J. Geophys. Res.-Atmos., 126, e2021JD034809, https://doi.org/10.1029/2021JD034809, 2021.
McCabe, J. R., Thiemens, M. H., and Savarino, J.: A record of ozone variability in South Pole Antarctic snow: Role of nitrate oxygen isotopes, J. Geophys. Res., 112, D12303, https://doi.org/10.1029/2006JD007822, 2007.
Michalski, G., and Bhattacharya, S. K.: The role of symmetry in the mass independent isotope effect in ozone, P. Natl. Acad. Sci. USA, 106, 5493–5496, https://doi.org/10.1073/pnas.0812755106, 2009.
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 molecules, 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.
Miller, D. J., Chai, J., Guo, F., Dell, C. J., Karsten, H., and Hastings, M.
G: Isotopic Composition of In Situ Soil NOx Emissions in
Manure-Fertilized Cropland, Geophys. Res. Lett., 45, 12058–12066,
https://doi.org/10.1029/2018GL079619, 2018.
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.
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.
Morin, S., Erbland, J., Savarino, J., Domine, F., Bock, J., Friess, U.,
Jacobi, H.-W., Sihler, H., and Martins, J. M. F.: An isotopic view on the
connection between photolytic emissions of NOx from the Arctic snowpack
and its oxidation by reactive halogens, J. Geophys. Res., 117, D00R08,
https://doi.org/10.1029/2011JD016618, 2012.
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.
Obbard, R. W.: Microplastics in Polar Regions: The role of long range
transport, Curr. Opin. Environ. Sci., 1, 24–29,
https://doi.org/10.1016/j.coesh.2017.10.004, 2018.
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.
Parsons, T. R., Maita, Y., and Lalli, C. M.: A Manual of Chemical and Biological Methods for Seawater Analysis Pergamon, Pergamon Press, Oxford, 7–9, https://doi.org/10.25607/OBP-1830, 1984.
Paton-Walsh, C., Emmerson, K. M., Garland, R. M., Keywood, M., Hoelzemann,
J. J., Huneeus, N., Buchholz, R. R., Humphries, R. S., Altieri, K., Schmale,
J., Wilson, S. R., Labuschagne, C., Kalisa, E., Fisher, J. A., Deutscher, N.
M., van Zyl, P. G., Beukes, J. P., Joubert, W., Martin, L., Mkololo, T.,
Barbosa, C., Anrade, M. de F., Schofield, R., Mallet, M. D., Harvey, M. J.,
Formenti, P., Piketh, S. J., and Olivares, G.: Key challenges for
tropospheric chemistry in the Southern Hemisphere, Elem. Sci. Anth., 10,
1–35, https://doi.org/10.1525/elementa.2021.00050, 2022.
Reed, C., Evans, M. J., Crilley, L. R., Bloss, W. J., Sherwen, T., Read, K. A., Lee, J. D., and Carpenter, L. J.: Evidence for renoxification in the tropical marine boundary layer, Atmos. Chem. Phys., 17, 4081–4092, https://doi.org/10.5194/acp-17-4081-2017, 2017.
Rolph, G., Stein, A., and Stunder, B.: Real-time environmental applications and display system: READY, Environ. Model. Softw., 95, 210–228, https://doi.org/10.1016/j.envsoft.2017.06.025, 2017.
Romer, P. S., Wooldridge, P. J., Crounse, J. D., Kim, M. J., Wennberg, P.
O., Dibb, J. E., Scheuer, E., Blake, D. R., Meinardi, S., Brosius, A. L.,
Thames, A. B., Miller, D. O., Brune, W. H., Hall, S. R., Ryerson, T. B., and
Cohen, R. C.: Constraints on Aerosol Nitrate Photolysis as a Potential
Source of HONO and NOx, Environ. Sci. Technol., 52, 13738–13746,
https://doi.org/10.1021/acs.est.8b03861, 2018.
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., 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.
Savoie, D. L., Prospero, J. M., Larsen, R. J., Haung, F., Izaguirre, M. A., Haung, T., Snowdon, T. H., Custals, L., and Sanderson, C. G.: Nitrogen and Sulphur Species in Antarctic Aerosols at Mawson, Palmer Station, and Marsh (King George Island), J. Atmos. Chem., 17, 95–122, https://doi.org/10.1007/BF00702821, 1993.
Schmale, J., Baccarini, A., Thurnherr, I., Henning, S., Efraim, A., Regayre,
L., Bolas, C., Hartmann, M., Welti, A., Lehtipalo, K., Aemisegger, F.,
Tatzelt, C., Landwehr, S., Modini, R. L., Tummon, F., Johnson, J. S.,
Harris, N., Schnaiter, M., Toffoli, A., Derkani. M., Bukowiecki, N.,
Stratmann, F., Dommen, J., Baltensperger, U., Wernli, H., Rosenfeld, D.,
Gysel-Beer, M., and Carslaw, K. S.: Overview of the Antarctic
Circumnavigation Expedition: study of preindustrial-like aerosols and their
climate effects (ACE-SPACE), B. Am. Meteorol. Soc., 100, 2260–2283, 2019.
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., Ma, H., Hu, Z., Sun, B., Li, C., Yu, J., Ma, T., An,
C., Jiang, S., Li, Y., and Hastings, M. G.: Distinguishing summertime
atmospheric 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.
Shi, G., Li, C., Li, Y., Chen, Z., Ging, M., Ma, H., Jiang, S., An, C., Guo,
J., Sun, B., and Hastings, M. Q.: Isotopic constraints on sources,
production, and phase partitioning for nitrate in the atmosphere and
snowfall in coastal East Antarctica, Earth Planet. Sc. Lett., 578,
1–12, https://doi.org/10.1016/j.epsl.2021.117300, 2022.
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.
Strickland, J. D. H. and Parsons, T. R.: A practical handbook of seawater analysis, 2nd Edn., B. Fish. Res. Board Can., 167, 77–80, https://doi.org/10.25607/OBP-1791, 1972.
Theys, N., Van Roozendael, M., Hendrick, F., Yang, X., De Smedt, I., Richter, A., Begoin, M., Errera, Q., Johnston, P. V., Kreher, K., and De Mazière, M.: Global observations of tropospheric BrO columns using GOME-2 satellite data, Atmos. Chem. Phys., 11, 1791–1811, https://doi.org/10.5194/acp-11-1791-2011, 2011.
Thiemens, M. H.: History and Applications of Mass-Independent Isotope
Effects, Annu. Rev. Earth Planet. Sci., 34, 217–262,
https://doi.org/10.1146/annurev.earth.34.031405.125026, 2006.
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.
von Savigny, C., Ulasi, E. P., Eichmann, K.-U., Bovensmann, H., and Burrows, J. P.: Detection and mapping of polar stratospheric clouds using limb scattering observations, Atmos. Chem. Phys., 5, 3071–3079, https://doi.org/10.5194/acp-5-3071-2005, 2005.
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, https://doi.org/10.1029/97JD03364, 1998.
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 dynamic 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.
Wang, Z., Stephens, G., Deshler, T., Trepre, C., Parish, T., Vane, D.,
Winker, D., Liu, D., and Adhikari, L.: Association of Antarctic polar
stratospheric cloud formation on tropospheric cloud systems, Geophys. Res.
Lett., 35, L13806, https://doi.org/10.1029/2008GL034209, 2008.
Winton, V. H. L., Ming, A., Caillon, N., Hauge, L., Jones, A. E., Savarino, J., Yang, X., and Frey, M. M.: Deposition, recycling, and archival of nitrate stable isotopes between the air–snow interface: comparison between Dronning Maud Land and Dome C, Antarctica, Atmos. Chem. Phys., 20, 5861–5885, https://doi.org/10.5194/acp-20-5861-2020, 2020.
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, https://doi.org/10.5194/acp-8-5627-2008, 2008.
Yang, X., Pyle, J. A., Cox, R. A., Theys, N., and Van Roozendael, M.: Snow-sourced bromine and its implications for polar tropospheric ozone, Atmos. Chem. Phys., 10, 7763–7773, https://doi.org/10.5194/acp-10-7763-2010, 2010.
Ye, C., Zhou, X., Pu, D., Stutz, J., Festa, J., Spolaor, M., Tsai, C.,
Cantrell, C., Mauldin III, R. L., Campos, T., Weinheimer, A., Hornbrook, R.
S., Apel, E. C., Guenther, A., Kaser, L., Yuan, B., Karl, T., Haggerty, J.,
Hall, S., Ullmann, K., Smith, J. N., Ortega, J., and Christoph, K.: Rapid
cycling of reactive nitrogen in the marine boundary layer, Nature, 532,
489–491, https://doi.org/10.1038/nature17195, 2016.
Zhou, X., Gao, H., He, Y., Huang, G., Bertman, S. B., Civerolo, K., and
Schwab, J.: Nitric acid photolysis on surfaces in low-NOx environments:
Significant atmospheric implications, Geophys. Res. Lett., 23, 2217,
https://doi.org/10.1029/2003GL018620, 2003.
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
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.
A seasonal analysis of the nitrogen isotopes of atmospheric nitrate over the remote Southern...
Altmetrics
Final-revised paper
Preprint