Articles | Volume 23, issue 7
https://doi.org/10.5194/acp-23-4185-2023
© 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-23-4185-2023
© Author(s) 2023. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
06 Apr 2023
Research article |
| 06 Apr 2023
| 06 Apr 2023
Nitrate chemistry in the northeast US – Part 1: Nitrogen isotope seasonality tracks nitrate formation chemistry
Claire Bekker
Department of Earth, Environmental, and Planetary Sciences, Brown
University, Providence, RI 02912, USA
now at: Department of Environmental Health Sciences, University of
California Los Angeles, Los Angeles, CA 90095, USA
Wendell W. Walters
CORRESPONDING AUTHOR
Institute at Brown for Environment and Society, Brown University,
Providence, RI 02912, USA
now at: Department of Chemistry and Biochemistry, University of South Carolina, Columbia, SC 29208, USA
Lee T. Murray
Department of Earth and Environmental Sciences, University of
Rochester, Rochester, NY 14627, USA
Meredith G. Hastings
Department of Earth, Environmental, and Planetary Sciences, Brown
University, Providence, RI 02912, USA
Institute at Brown for Environment and Society, Brown University,
Providence, RI 02912, USA
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Michael J. Prather, Xin Zhu, Clare M. Flynn, Sarah A. Strode, Jose M. Rodriguez, Stephen D. Steenrod, Junhua Liu, Jean-Francois Lamarque, Arlene M. Fiore, Larry W. Horowitz, Jingqiu Mao, Lee T. Murray, Drew T. Shindell, and Steven C. Wofsy
Atmos. Chem. Phys., 17, 9081–9102, https://doi.org/10.5194/acp-17-9081-2017, https://doi.org/10.5194/acp-17-9081-2017, 2017
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Lu Shen, Loretta J. Mickley, and Lee T. Murray
Atmos. Chem. Phys., 17, 4355–4367, https://doi.org/10.5194/acp-17-4355-2017, https://doi.org/10.5194/acp-17-4355-2017, 2017
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The Cryosphere Discuss., https://doi.org/10.5194/tc-2016-163, https://doi.org/10.5194/tc-2016-163, 2016
Revised manuscript not accepted
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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
L. T. Murray, L. J. Mickley, J. O. Kaplan, E. D. Sofen, M. Pfeiffer, and B. Alexander
Atmos. Chem. Phys., 14, 3589–3622, https://doi.org/10.5194/acp-14-3589-2014, https://doi.org/10.5194/acp-14-3589-2014, 2014
Related subject area
Subject: Isotopes | Research Activity: Field Measurements | Altitude Range: Troposphere | Science Focus: Chemistry (chemical composition and reactions)
A seasonal analysis of aerosol NO3− sources and NOx oxidation pathways in the Southern Ocean marine boundary layer
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
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
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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.
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
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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
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Nitrate isotopes in Antarctic ice do not preserve the seasonal isotopic cycles of the atmosphere, which limits their use to study the past. We studied nitrate along an 850 km Antarctic transect to learn how these cycles are changed by sunlight-driven chemistry in the snow. Our findings suggest that the snow accumulation rate and other environmental signals can be extracted from nitrate with the right sampling and analytical approaches.
Bryce F. J. Kelly, Xinyi Lu, Stephen J. Harris, Bruno G. Neininger, Jorg M. Hacker, Stefan Schwietzke, Rebecca E. Fisher, James L. France, Euan G. Nisbet, David Lowry, Carina van der Veen, Malika Menoud, and Thomas Röckmann
Atmos. Chem. Phys., 22, 15527–15558, https://doi.org/10.5194/acp-22-15527-2022, https://doi.org/10.5194/acp-22-15527-2022, 2022
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This study explores using the composition of methane of in-flight atmospheric air samples for greenhouse gas inventory verification. The air samples were collected above one of the largest coal seam gas production regions in the world. Adjacent to these gas fields are coal mines, Australia's largest cattle feedlot, and over 1 million grazing cattle. The results are also used to identify methane mitigation opportunities.
Malika Menoud, Carina van der Veen, Jaroslaw Necki, Jakub Bartyzel, Barbara Szénási, Mila Stanisavljević, Isabelle Pison, Philippe Bousquet, and Thomas Röckmann
Atmos. Chem. Phys., 21, 13167–13185, https://doi.org/10.5194/acp-21-13167-2021, https://doi.org/10.5194/acp-21-13167-2021, 2021
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Using measurements of methane isotopes in ambient air and a 3D atmospheric transport model, in Krakow, Poland, we mainly detected fossil-fuel-related sources, coming from coal mining in Silesia and from the use of natural gas in the city. Emission inventories report large emissions from coal mine activity in Silesia, which is in agreement with our measurements. However, methane sources in the urban area of Krakow related to the use of fossil fuels might be underestimated in the inventories.
Xinyi Lu, Stephen J. Harris, Rebecca E. Fisher, James L. France, Euan G. Nisbet, David Lowry, Thomas Röckmann, Carina van der Veen, Malika Menoud, Stefan Schwietzke, and Bryce F. J. Kelly
Atmos. Chem. Phys., 21, 10527–10555, https://doi.org/10.5194/acp-21-10527-2021, https://doi.org/10.5194/acp-21-10527-2021, 2021
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Many coal seam gas (CSG) facilities in the Surat Basin, Australia, are adjacent to other sources of methane, including agricultural, urban, and natural seeps. This makes it challenging to estimate the amount of methane being emitted into the atmosphere from CSG facilities. This research demonstrates that measurements of the carbon and hydrogen stable isotopic composition of methane can distinguish between and apportion methane emissions from CSG facilities, cattle, and many other sources.
Sarah Albertin, Joël Savarino, Slimane Bekki, Albane Barbero, and Nicolas Caillon
Atmos. Chem. Phys., 21, 10477–10497, https://doi.org/10.5194/acp-21-10477-2021, https://doi.org/10.5194/acp-21-10477-2021, 2021
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We report an efficient method to collect atmospheric NO2 adapted for multi-isotopic analysis and present the first NO2 triple oxygen and double nitrogen isotope measurements. Atmospheric samplings carried out in Grenoble, France, highlight the NO2 isotopic signature sensitivity to the local NOx emissions and chemical regimes. These preliminary results are very promising for using the combination of Δ17O and δ15N of NO2 as a probe of the atmospheric NOx emissions and chemistry.
Ana Moreno, Miguel Iglesias, Cesar Azorin-Molina, Carlos Pérez-Mejías, Miguel Bartolomé, Carlos Sancho, Heather Stoll, Isabel Cacho, Jaime Frigola, Cinta Osácar, Arsenio Muñoz, Antonio Delgado-Huertas, Ileana Bladé, and Françoise Vimeux
Atmos. Chem. Phys., 21, 10159–10177, https://doi.org/10.5194/acp-21-10159-2021, https://doi.org/10.5194/acp-21-10159-2021, 2021
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We present a large and unique dataset of the rainfall isotopic composition at seven sites from northern Iberia to characterize their variability at daily and monthly timescales and to assess the role of climate and geographic factors in the modulation of δ18O values. We found that the origin, moisture uptake along the trajectory and type of precipitation play a key role. These results will help to improve the interpretation of δ18O paleorecords from lacustrine carbonates or speleothems.
Kun Wang, Shohei Hattori, Mang Lin, Sakiko Ishino, Becky Alexander, Kazuki Kamezaki, Naohiro Yoshida, and Shichang Kang
Atmos. Chem. Phys., 21, 8357–8376, https://doi.org/10.5194/acp-21-8357-2021, https://doi.org/10.5194/acp-21-8357-2021, 2021
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Sulfate aerosols play an important climatic role and exert adverse effects on the ecological environment and human health. In this study, we present the triple oxygen isotopic composition of sulfate from the Mt. Everest region, southern Tibetan Plateau, and decipher the formation mechanisms of atmospheric sulfate in this pristine environment. The results indicate the important role of the S(IV) + O3 pathway in atmospheric sulfate formation promoted by conditions of high cloud water pH.
Pete D. Akers, Ben G. Kopec, Kyle S. Mattingly, Eric S. Klein, Douglas Causey, and Jeffrey M. Welker
Atmos. Chem. Phys., 20, 13929–13955, https://doi.org/10.5194/acp-20-13929-2020, https://doi.org/10.5194/acp-20-13929-2020, 2020
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Water vapor isotopes recorded for 2 years in coastal northern Greenland largely reflect changes in sea ice cover, with distinct values when Baffin Bay is ice covered in winter vs. open in summer. Resulting changes in moisture transport, surface winds, and air temperature also modify the isotopes. Local glacial ice may thus preserve past changes in the Baffin Bay sea ice extent, and this will help us better understand how the Arctic environment and water cycle responds to global climate change.
Ben Yu, Lin Yang, Linlin Wang, Hongwei Liu, Cailing Xiao, Yong Liang, Qian Liu, Yongguang Yin, Ligang Hu, Jianbo Shi, and Guibin Jiang
Atmos. Chem. Phys., 20, 9713–9723, https://doi.org/10.5194/acp-20-9713-2020, https://doi.org/10.5194/acp-20-9713-2020, 2020
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We found that Br atoms in the marine boundary layer are the most probable oxidizer that transform gaseous elemental mercury into gaseous oxidized mercury, according to the mercury isotopes in the total gaseous mercury. On the other hand, Br or Cl atoms are not the primary oxidizers that produced oxidized mercury on particles. This study showed that mercury isotopes can provide new evidence that help us to fully understand the transformations of atmospheric mercury.
Longfei Yu, Eliza Harris, Stephan Henne, Sarah Eggleston, Martin Steinbacher, Lukas Emmenegger, Christoph Zellweger, and Joachim Mohn
Atmos. Chem. Phys., 20, 6495–6519, https://doi.org/10.5194/acp-20-6495-2020, https://doi.org/10.5194/acp-20-6495-2020, 2020
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We observed the isotopic composition of nitrous oxide in the unpolluted air at Jungfraujoch for 5 years. Our results indicate a clear seasonal pattern in the isotopic composition, corresponding with that in atmospheric nitrous oxide levels. This is most likely due to temporal variations in both emission processes and air mass sources for Jungfraujoch. Our findings are of importance to global nitrous oxide modelling and to better understanding of long-term trends in atmospheric nitrous oxide.
V. Holly L. Winton, Alison Ming, Nicolas Caillon, Lisa Hauge, Anna E. Jones, Joel Savarino, Xin Yang, and Markus M. Frey
Atmos. Chem. Phys., 20, 5861–5885, https://doi.org/10.5194/acp-20-5861-2020, https://doi.org/10.5194/acp-20-5861-2020, 2020
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The transfer of the nitrogen stable isotopic composition in nitrate between the air and snow at low accumulation sites in Antarctica leaves an UV imprint in the snow. Quantifying how nitrate isotope values change allows us to interpret longer ice core records. Based on nitrate observations and modelling at Kohnen, East Antarctica, the dominant factors controlling the nitrate isotope signature in deep snow layers are the depth of light penetration into the snowpack and the snow accumulation rate.
Isabelle Genot, David Au Yang, Erwan Martin, Pierre Cartigny, Erwann Legendre, and Marc De Rafelis
Atmos. Chem. Phys., 20, 4255–4273, https://doi.org/10.5194/acp-20-4255-2020, https://doi.org/10.5194/acp-20-4255-2020, 2020
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Given their critical impact on radiative forcing, sulfate aerosols have been extensively studied using their isotope signatures (δ34S, ∆33S, ∆36S, δ18O, and ∆17O). A striking observation is that ∆33S > 0 ‰, implying a missing reservoir in the sulfur cycle. Here, we measured ∆33S < 0 ‰ in black crust sulfates (i.e., formed on carbonate walls) that must therefore result from distinct chemical pathway(s) compared to sulfate aerosols, and they may well represent this complementary reservoir.
Angelina Wenger, Katherine Pugsley, Simon O'Doherty, Matt Rigby, Alistair J. Manning, Mark F. Lunt, and Emily D. White
Atmos. Chem. Phys., 19, 14057–14070, https://doi.org/10.5194/acp-19-14057-2019, https://doi.org/10.5194/acp-19-14057-2019, 2019
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We present 14CO2 observations at a background site in Ireland and a tall tower site in the UK. These data have been used to calculate the contribution of fossil fuel sources to atmospheric CO2 mole fractions from the UK and Ireland. 14CO2 emissions from nuclear industry sites in the UK cause a higher uncertainty in the results compared to observations in other locations. The observed ffCO2 at the site was not significantly different from simulated values based on the bottom-up inventory.
Isaac J. Vimont, Jocelyn C. Turnbull, Vasilii V. Petrenko, Philip F. Place, Colm Sweeney, Natasha Miles, Scott Richardson, Bruce H. Vaughn, and James W. C. White
Atmos. Chem. Phys., 19, 8547–8562, https://doi.org/10.5194/acp-19-8547-2019, https://doi.org/10.5194/acp-19-8547-2019, 2019
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Stable isotopes of Carbon Monoxide (CO) and radiocarbon carbon dioxide were measured over three summers at Indianapolis, Indiana, US, and for 1 year at a site thought to be strongly influenced by CO from oxidized volatile organic compounds (VOCs) in South Carolina, US. The Indianapolis results were used to provide an estimate of the carbon and oxygen isotopic signatures of CO produced from oxidized VOCs. This updated estimate agrees well with the data from South Carolina during the summer.
David Au Yang, Pierre Cartigny, Karine Desboeufs, and David Widory
Atmos. Chem. Phys., 19, 3779–3796, https://doi.org/10.5194/acp-19-3779-2019, https://doi.org/10.5194/acp-19-3779-2019, 2019
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Sulfates present in urban aerosols collected worldwide usually exhibit 33S-anomalies whose origin remains unclear. Besides, the sulfate concentration is not very well modelled nowadays, which, coupled with the isotopic composition anomaly on the 33S, would highlight the presence of at least an additional oxidation pathway, different from O2+TMI, O3, OH, H2O2 and NO2. We suggest here the implication of two other possible oxidation pathways.
Martine M. Savard, Amanda S. Cole, Robert Vet, and Anna Smirnoff
Atmos. Chem. Phys., 18, 10373–10389, https://doi.org/10.5194/acp-18-10373-2018, https://doi.org/10.5194/acp-18-10373-2018, 2018
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Improving air quality requires understanding of the atmospheric processes transforming nitrous oxides emitted by human activities into nitrates, an N form that may degrade natural ecosystems. Isotopes (∆17O, δ18O) are characterized in separate wet, particulate and gaseous nitrates for the first time. The gas ranges are distinct from those of the other nitrates, and the plume dynamics emerge as crucial in interpreting the results, which unravel key processes behind the distribution of nitrates.
Sergey Gromov, Carl A. M. Brenninkmeijer, and Patrick Jöckel
Atmos. Chem. Phys., 18, 9831–9843, https://doi.org/10.5194/acp-18-9831-2018, https://doi.org/10.5194/acp-18-9831-2018, 2018
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Using the observational data on 13C (CO) and 13C (CH4) from the extra-tropical Southern Hemisphere (ETSH) and EMAC model we (1) provide an independent, observation-based evaluation of Cl atom concentration variations in the ETSH throughout 1994–2000, (2) show that the role of tropospheric Cl as a sink of CH4 is seriously overestimated in the literature, (3) demonstrate that the 13C/12C ratio of CO is a sensitive indicator for the isotopic composition of reacted CH4 and therefore for its sources.
Richard P. Fiorella, Ryan Bares, John C. Lin, James R. Ehleringer, and Gabriel J. Bowen
Atmos. Chem. Phys., 18, 8529–8547, https://doi.org/10.5194/acp-18-8529-2018, https://doi.org/10.5194/acp-18-8529-2018, 2018
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Fossil fuel combustion produces water; where fossil fuel combustion is concentrated in urban areas, this humidity source may represent ~ 10 % of total humidity. In turn, this water vapor addition may alter urban meteorology, though the contribution of combustion vapor is difficult to measure. Using stable water isotopes, we estimate that up to 16 % of urban humidity may arise from combustion when the atmosphere is stable during winter, and develop recommendations for application in other cities.
Neda Amiri, Roya Ghahreman, Ofelia Rempillo, Travis W. Tokarek, Charles A. Odame-Ankrah, Hans D. Osthoff, and Ann-Lise Norman
Atmos. Chem. Phys., 18, 7757–7780, https://doi.org/10.5194/acp-18-7757-2018, https://doi.org/10.5194/acp-18-7757-2018, 2018
David M. Nelson, Urumu Tsunogai, Dong Ding, Takuya Ohyama, Daisuke D. Komatsu, Fumiko Nakagawa, Izumi Noguchi, and Takashi Yamaguchi
Atmos. Chem. Phys., 18, 6381–6392, https://doi.org/10.5194/acp-18-6381-2018, https://doi.org/10.5194/acp-18-6381-2018, 2018
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Atmospheric nitrate may be produced locally and/or come from upwind regions. To address this issue we measured oxygen and nitrogen isotopes of wet and dry nitrate deposition at nearby urban and rural sites. Our results suggest that, relative to nitrate in wet deposition in urban environments and wet and dry deposition in rural environments, nitrate in dry deposition in urban environments results from local NOx emissions more so than wet deposition, which is transported longer distances.
Pengzhen He, Becky Alexander, Lei Geng, Xiyuan Chi, Shidong Fan, Haicong Zhan, Hui Kang, Guangjie Zheng, Yafang Cheng, Hang Su, Cheng Liu, and Zhouqing Xie
Atmos. Chem. Phys., 18, 5515–5528, https://doi.org/10.5194/acp-18-5515-2018, https://doi.org/10.5194/acp-18-5515-2018, 2018
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We use observations of the oxygen isotopic composition of sulfate aerosol as a fingerprint to quantify various sulfate formation mechanisms during pollution events in Beijing, China. We found that heterogeneous reactions on aerosols dominated sulfate production in general; however, in-cloud reactions would dominate haze sulfate production when cloud liquid water content was high. The findings also suggest the heterogeneity of aerosol acidity should be parameterized in models.
Tesfaye A. Berhanu, Sönke Szidat, Dominik Brunner, Ece Satar, Rüdiger Schanda, Peter Nyfeler, Michael Battaglia, Martin Steinbacher, Samuel Hammer, and Markus Leuenberger
Atmos. Chem. Phys., 17, 10753–10766, https://doi.org/10.5194/acp-17-10753-2017, https://doi.org/10.5194/acp-17-10753-2017, 2017
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Fossil fuel CO2 is the major contributor of anthropogenic CO2 in the atmosphere, and accurate quantification is essential to better understand the carbon cycle. Such accurate quantification can be conducted based on radiocarbon measurements. In this study, we present radiocarbon measurements from a tall tower site in Switzerland. From these measurements, we have observed seasonally varying fossil fuel CO2 contributions and a biospheric CO2 component that varies diurnally and seasonally.
Markella Prokopiou, Patricia Martinerie, Célia J. Sapart, Emmanuel Witrant, Guillaume Monteil, Kentaro Ishijima, Sophie Bernard, Jan Kaiser, Ingeborg Levin, Thomas Blunier, David Etheridge, Ed Dlugokencky, Roderik S. W. van de Wal, and Thomas Röckmann
Atmos. Chem. Phys., 17, 4539–4564, https://doi.org/10.5194/acp-17-4539-2017, https://doi.org/10.5194/acp-17-4539-2017, 2017
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Nitrous oxide is the third most important anthropogenic greenhouse gas with an increasing mole fraction. To understand its natural and anthropogenic sources
we employ isotope measurements. Results show that while the N2O mole fraction increases, its heavy isotope content decreases. The isotopic changes observed underline the dominance of agricultural emissions especially at the early part of the record, whereas in the later decades the contribution from other anthropogenic sources increases.
Sakiko Ishino, Shohei Hattori, Joel Savarino, Bruno Jourdain, Susanne Preunkert, Michel Legrand, Nicolas Caillon, Albane Barbero, Kota Kuribayashi, and Naohiro Yoshida
Atmos. Chem. Phys., 17, 3713–3727, https://doi.org/10.5194/acp-17-3713-2017, https://doi.org/10.5194/acp-17-3713-2017, 2017
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We show the first simultaneous observations of triple oxygen isotopic compositions of atmospheric sulfate, nitrate, and ozone at Dumont d'Urville, coastal Antarctica. The contrasting seasonal trends between oxygen isotopes of ozone and those of sulfate and nitrate indicate that these signatures in sulfate and nitrate are mainly controlled by changes in oxidation chemistry. We also discuss the specific oxidation chemistry induced by the unique phenomena at the site.
Giulia Zazzeri, Dave Lowry, Rebecca E. Fisher, James L. France, Mathias Lanoisellé, Bryce F. J. Kelly, Jaroslaw M. Necki, Charlotte P. Iverach, Elisa Ginty, Miroslaw Zimnoch, Alina Jasek, and Euan G. Nisbet
Atmos. Chem. Phys., 16, 13669–13680, https://doi.org/10.5194/acp-16-13669-2016, https://doi.org/10.5194/acp-16-13669-2016, 2016
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Methane emissions estimates from the coal sector are highly uncertain. Precise δ13C isotopic signatures of methane sources can be used in atmospheric models for a methane budget assessment. Emissions from both underground and opencast coal mines in the UK, Australia and Poland were sampled and isotopically characterised using high-precision measurements of δ13C values. Representative isotopic signatures were provided, taking into account specific ranks of coal and mine type.
Qiang Huang, Jiubin Chen, Weilin Huang, Pingqing Fu, Benjamin Guinot, Xinbin Feng, Lihai Shang, Zhuhong Wang, Zhongwei Wang, Shengliu Yuan, Hongming Cai, Lianfang Wei, and Ben Yu
Atmos. Chem. Phys., 16, 11773–11786, https://doi.org/10.5194/acp-16-11773-2016, https://doi.org/10.5194/acp-16-11773-2016, 2016
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Atmospheric airborne mercury is of particular concern because, once inhaled, both Hg and its vectors might have adverse effects on human beings. In this study, we attempted to identify the sources of PM2.5-Hg in Beijing, China, using Hg isotopic composition. Large range and seasonal variations in both mass-dependent and mass-independent fractionations of Hg isotopes in haze particles demonstrate the usefulness of Hg isotopes for directly tracing the sources and its vectors in the atmosphere.
Qianjie Chen, Lei Geng, Johan A. Schmidt, Zhouqing Xie, Hui Kang, Jordi Dachs, Jihong Cole-Dai, Andrew J. Schauer, Madeline G. Camp, and Becky Alexander
Atmos. Chem. Phys., 16, 11433–11450, https://doi.org/10.5194/acp-16-11433-2016, https://doi.org/10.5194/acp-16-11433-2016, 2016
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The formation mechanisms of sulfate in the marine boundary layer are not well understood, which could result in large uncertainties in aerosol radiative forcing. We measure the oxygen isotopic composition (Δ17O) of sulfate collected in the MBL and analyze with a global transport model. Our results suggest that 33–50 % of MBL sulfate is formed via oxidation of S(IV) by hypohalous acids HOBr / HOCl in the aqueous phase, and the daily-mean HOBr/HOCl concentrations are on the order of 0.01–0.1 ppt.
Thomas Röckmann, Simon Eyer, Carina van der Veen, Maria E. Popa, Béla Tuzson, Guillaume Monteil, Sander Houweling, Eliza Harris, Dominik Brunner, Hubertus Fischer, Giulia Zazzeri, David Lowry, Euan G. Nisbet, Willi A. Brand, Jaroslav M. Necki, Lukas Emmenegger, and Joachim Mohn
Atmos. Chem. Phys., 16, 10469–10487, https://doi.org/10.5194/acp-16-10469-2016, https://doi.org/10.5194/acp-16-10469-2016, 2016
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A dual isotope ratio mass spectrometric system (IRMS) and a quantum cascade laser absorption spectroscopy (QCLAS)-based technique were deployed at the Cabauw experimental site for atmospheric research (CESAR) in the Netherlands and performed in situ, high-frequency (approx. hourly) measurements for a period of more than 5 months, yielding a combined dataset with more than 2500 measurements of both δ13C and δD.
Joël Savarino, William C. Vicars, Michel Legrand, Suzanne Preunkert, Bruno Jourdain, Markus M. Frey, Alexandre Kukui, Nicolas Caillon, and Jaime Gil Roca
Atmos. Chem. Phys., 16, 2659–2673, https://doi.org/10.5194/acp-16-2659-2016, https://doi.org/10.5194/acp-16-2659-2016, 2016
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Atmospheric nitrate is collected on the East Antarctic ice sheet. Nitrogen and oxygen stable isotopes and concentrations of nitrate are measured. Using a box model, we show that there is s systematic discrepancy between observations and model results. We suggest that this discrepancy probably results from unknown NOx chemistry above the Antarctic ice sheet. However, possible misconception in the stable isotope mass balance is not completely excluded.
T. A. Berhanu, J. Savarino, J. Erbland, W. C. Vicars, S. Preunkert, J. F. Martins, and M. S. Johnson
Atmos. Chem. Phys., 15, 11243–11256, https://doi.org/10.5194/acp-15-11243-2015, https://doi.org/10.5194/acp-15-11243-2015, 2015
Short summary
Short summary
In this field study at Dome C, Antarctica, we investigated the effect of solar UV photolysis on the stable isotopes of nitrate in snow via comparison of two identical snow pits while exposing only one to solar UV. From the difference between the average isotopic fractionations calculated for each pit, we determined a purely photolytic nitrogen isotopic fractionation of -55.8‰, in good agreement with what has been recently determined in a laboratory study.
M. Saccon, A. Kornilova, L. Huang, S. Moukhtar, and J. Rudolph
Atmos. Chem. Phys., 15, 10825–10838, https://doi.org/10.5194/acp-15-10825-2015, https://doi.org/10.5194/acp-15-10825-2015, 2015
E. D. Sofen, B. Alexander, E. J. Steig, M. H. Thiemens, S. A. Kunasek, H. M. Amos, A. J. Schauer, M. G. Hastings, J. Bautista, T. L. Jackson, L. E. Vogel, J. R. McConnell, D. R. Pasteris, and E. S. Saltzman
Atmos. Chem. Phys., 14, 5749–5769, https://doi.org/10.5194/acp-14-5749-2014, https://doi.org/10.5194/acp-14-5749-2014, 2014
J. Wintel, E. Hösen, R. Koppmann, M. Krebsbach, A. Hofzumahaus, and F. Rohrer
Atmos. Chem. Phys., 13, 11059–11071, https://doi.org/10.5194/acp-13-11059-2013, https://doi.org/10.5194/acp-13-11059-2013, 2013
F. A. Haumann, A. M. Batenburg, G. Pieterse, C. Gerbig, M. C. Krol, and T. Röckmann
Atmos. Chem. Phys., 13, 9401–9413, https://doi.org/10.5194/acp-13-9401-2013, https://doi.org/10.5194/acp-13-9401-2013, 2013
C. J. Sapart, P. Martinerie, E. Witrant, J. Chappellaz, R. S. W. van de Wal, P. Sperlich, C. van der Veen, S. Bernard, W. T. Sturges, T. Blunier, J. Schwander, D. Etheridge, and T. Röckmann
Atmos. Chem. Phys., 13, 6993–7005, https://doi.org/10.5194/acp-13-6993-2013, https://doi.org/10.5194/acp-13-6993-2013, 2013
J. Erbland, W. C. Vicars, J. Savarino, S. Morin, M. M. Frey, D. Frosini, E. Vince, and J. M. F. Martins
Atmos. Chem. Phys., 13, 6403–6419, https://doi.org/10.5194/acp-13-6403-2013, https://doi.org/10.5194/acp-13-6403-2013, 2013
A. Guillon, K. Le Ménach, P.-M. Flaud, N. Marchand, H. Budzinski, and E. Villenave
Atmos. Chem. Phys., 13, 2703–2719, https://doi.org/10.5194/acp-13-2703-2013, https://doi.org/10.5194/acp-13-2703-2013, 2013
D. Ceburnis, A. Garbaras, S. Szidat, M. Rinaldi, S. Fahrni, N. Perron, L. Wacker, S. Leinert, V. Remeikis, M. C. Facchini, A. S. H. Prevot, S. G. Jennings, M. Ramonet, and C. D. O'Dowd
Atmos. Chem. Phys., 11, 8593–8606, https://doi.org/10.5194/acp-11-8593-2011, https://doi.org/10.5194/acp-11-8593-2011, 2011
A. M. Batenburg, S. Walter, G. Pieterse, I. Levin, M. Schmidt, A. Jordan, S. Hammer, C. Yver, and T. Röckmann
Atmos. Chem. Phys., 11, 6985–6999, https://doi.org/10.5194/acp-11-6985-2011, https://doi.org/10.5194/acp-11-6985-2011, 2011
B. Tuzson, S. Henne, D. Brunner, M. Steinbacher, J. Mohn, B. Buchmann, and L. Emmenegger
Atmos. Chem. Phys., 11, 1685–1696, https://doi.org/10.5194/acp-11-1685-2011, https://doi.org/10.5194/acp-11-1685-2011, 2011
Y. T. Fang, K. Koba, X. M. Wang, D. Z. Wen, J. Li, Y. Takebayashi, X. Y. Liu, and M. Yoh
Atmos. Chem. Phys., 11, 1313–1325, https://doi.org/10.5194/acp-11-1313-2011, https://doi.org/10.5194/acp-11-1313-2011, 2011
S. S. Assonov, C. A. M. Brenninkmeijer, T. J. Schuck, and P. Taylor
Atmos. Chem. Phys., 10, 8575–8599, https://doi.org/10.5194/acp-10-8575-2010, https://doi.org/10.5194/acp-10-8575-2010, 2010
U. Tsunogai, D. D. Komatsu, S. Daita, G. A. Kazemi, F. Nakagawa, I. Noguchi, and J. Zhang
Atmos. Chem. Phys., 10, 1809–1820, https://doi.org/10.5194/acp-10-1809-2010, https://doi.org/10.5194/acp-10-1809-2010, 2010
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.
Amos, H. M., Jacob, D. J., Holmes, C. D., Fisher, J. A., Wang, Q., Yantosca, R. M., Corbitt, E. S., Galarneau, E., Rutter, A. P., Gustin, M. S., Steffen, A., Schauer, J. J., Graydon, J. A., Louis, V. L. St., Talbot, R. W., Edgerton, E. S., Zhang, Y., and Sunderland, E. M.: Gas-particle partitioning of atmospheric Hg(II) and its effect on global mercury deposition, Atmos. Chem. Phys., 12, 591–603, https://doi.org/10.5194/acp-12-591-2012, 2012.
Atkinson, R., Baulch, D. L., Cox, R. A., Crowley, J. N., Hampson, R. F., Hynes, R. G., Jenkin, M. E., Rossi, M. J., and Troe, J.: Evaluated kinetic and photochemical data for atmospheric chemistry: Volume I - gas phase reactions of Ox, HOx, NOx and SOx species, Atmos. Chem. Phys., 4, 1461–1738, https://doi.org/10.5194/acp-4-1461-2004, 2004.
Bates, K. H. and Jacob, D. J.: A new model mechanism for atmospheric oxidation of isoprene: global effects on oxidants, nitrogen oxides, organic products, and secondary organic aerosol, Atmos. Chem. Phys., 19, 9613–9640, https://doi.org/10.5194/acp-19-9613-2019, 2019.
Bauer, S. E., Koch, D., Unger, N., Metzger, S. M., Shindell, D. T., and Streets, D. G.: Nitrate aerosols today and in 2030: a global simulation including aerosols and tropospheric ozone, Atmos. Chem. Phys., 7, 5043–5059, https://doi.org/10.5194/acp-7-5043-2007, 2007.
Baumgardner, Ralph E., Lavery, T. F., Rogers, C. M., and Isil, S. S.:
Estimates of the Atmospheric Deposition of Sulfur and Nitrogen Species:
Clean Air Status and Trends Network, 1990–2000, Environ. Sci. Technol., 36,
2614–2629, https://doi.org/10.1021/es011146g, 2002.
Benedict, K. B., Carrico, C. M., Kreidenweis, S. M., Schichtel, B., Malm, W.
C., and Collett Jr., J. L.: A seasonal nitrogen deposition budget for Rocky
Mountain National Park, Ecol. Appl., 23, 1156–1169,
https://doi.org/10.1890/12-1624.1, 2013.
Bey, I., Jacob, D. J., Yantosca, R. M., Logan, J. A., Field, B. D., Fiore,
A. M., Li, Q., Liu, H. Y., Mickley, L. J., and Schultz, M. G.: Global
modeling of tropospheric chemistry with assimilated meteorology: Model
description and evaluation, J. Geophys. Atmos., 106, 23073–23095,
https://doi.org/10.1029/2001JD000807, 2001.
Beyn, F., Matthias, V., and Dähnke, K.: Changes in atmospheric nitrate
deposition in Germany – An isotopic perspective, Environ. Pollut., 194,
1–10, https://doi.org/10.1016/j.envpol.2014.06.043, 2014.
Beyn, F., Matthias, V., Aulinger, A., and Dähnke, K.: Do N-isotopes in
atmospheric nitrate deposition reflect air pollution levels?, Atmos.
Environ., 107, 281–288, https://doi.org/10.1016/j.atmosenv.2015.02.057,
2015.
Bloss, W. J., Evans, M. J., Lee, J. D., Sommariva, R., Heard, D. E., and
Pilling, M. J.: The oxidative capacity of the troposphere: Coupling of field
measurements of OH and a global chemistry transport model, Faraday Discuss.,
130, 425–436, https://doi.org/10.1039/B419090D, 2005.
Böhlke, J. K., Gwinn, C. J., and Coplen, T. B.: New Reference Materials
for Nitrogen-Isotope-Ratio Measurements, Geostandard. Newslett., 17,
159–164, https://doi.org/10.1111/j.1751-908X.1993.tb00131.x, 1993.
Böhlke, 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 equilibration, Rapid Commun. Mass. Sp., 17,
1835–1846, https://doi.org/10.1002/rcm.1123, 2003.
Breider, T. J., Mickley, L. J., Jacob, D. J., Ge, C., Wang, J., Payer
Sulprizio, M., Croft, B., Ridley, D. A., McConnell, J. R., and Sharma, S.:
Multidecadal trends in aerosol radiative forcing over the Arctic:
Contribution of changes in anthropogenic aerosol to Arctic warming since
1980, J. Geophys. Atmos., 122, 3573–3594,
https://doi.org/10.1002/2016JD025321, 2017.
Carslaw, D. C. and Ropkins, K.: Openair – an R package for air quality data
analysis, Environ. Modell. Softw., 27, 52–61,
https://doi.org/10.1016/j.envsoft.2011.09.008, 2012.
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.
CASTNET Site Locations: https://www.epa.gov/castnet/castnet-site-locations,
last access: 7 February 2023.
Chang, Y., Zhang, Y., Tian, C., Zhang, S., Ma, X., Cao, F., Liu, X., Zhang, W., Kuhn, T., and Lehmann, M. F.: Nitrogen isotope fractionation during gas-to-particle conversion of NOx to NO
Chang, Y., Zhang, Y.-L., Li, J., Tian, C., Song, L., Zhai, X., Zhang, W., Huang, T., Lin, Y.-C., Zhu, C., Fang, Y., Lehmann, M. F., and Chen, J.: Isotopic constraints on the atmospheric sources and formation of nitrogenous species in clouds influenced by biomass burning, Atmos. Chem. Phys., 19, 12221–12234, https://doi.org/10.5194/acp-19-12221-2019, 2019.
Cheng, I., Zhang, L., Blanchard, P., Dalziel, J., and Tordon, R.: Concentration-weighted trajectory approach to identifying potential sources of speciated atmospheric mercury at an urban coastal site in Nova Scotia, Canada, Atmos. Chem. Phys., 13, 6031–6048, https://doi.org/10.5194/acp-13-6031-2013, 2013.
Clarke, J. F., Edgerton, E., and Martin, B. E.: Dry deposition calculations
for the clean air status and trends network, Atmos. Environ., 31,
3667–3678, https://doi.org/10.1016/S1352-2310(97)00141-6, 1997.
Delmas, R., Serça, D., and Jambert, C.: Global inventory of NOx
sources, Nutr. Cycl. Agroecosys., 48, 51–60,
https://doi.org/10.1023/A:1009793806086, 1997.
Dimitriou, K., Remoundaki, E., Mantas, E., and Kassomenos, P.: Spatial
distribution of source areas of PM2.5 by Concentration Weighted
Trajectory (CWT) model applied in PM2.5 concentration and composition
data, Atmos. Environ., 116, 138–145,
https://doi.org/10.1016/j.atmosenv.2015.06.021, 2015.
Ehn, M., Thornton, J. A., Kleist, E., Sipilä, M., Junninen, H.,
Pullinen, I., Springer, M., Rubach, F., Tillmann, R., and Lee, B.: A large
source of low-volatility secondary organic aerosol, Nature, 506, 476–479,
https://doi.org/10.1038/nature13032, 2014.
Elliott, E. M., Kendall, C., Wankel, S. D., Burns, D. 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.
Elliott, E. M., Kendall, C., Boyer, E. W., Burns, D. A., Lear, G. G.,
Golden, H. E., Harlin, K., Bytnerowicz, A., Butler, T. J., and Glatz, R.:
Dual nitrate isotopes in dry deposition: Utility for partitioning NOx
source contributions to landscape nitrogen deposition, J. Geophys.
Res.-Biogeo., 114, G04020, https://doi.org/10.1029/2008JG000889, 2009.
Environmental Protection Agency Clean Air Markets Division Clean Air Status and Trends Network (CASTNET): Filter Pack Concentrations – Weekly, https://www.epa.gov/castnet, last access: 4 March 2022.
Fang, H., Walters, W. W., Mase, D., and Michalski, G.: iNRACM: incorporating 15N into the Regional Atmospheric Chemistry Mechanism (RACM) for assessing the role photochemistry plays in controlling the isotopic composition of NOx, NOy, and atmospheric nitrate, Geosci. Model Dev., 14, 5001–5022, https://doi.org/10.5194/gmd-14-5001-2021, 2021.
Felix, J. D., Elliott, E. M., and Shaw, S. L.: Nitrogen Isotopic Composition
of Coal-Fired Power Plant NOx: Influence of Emission Controls and
Implications for Global Emission Inventories, Environ. Sci. Technol., 46,
3528–3535, https://doi.org/10.1021/es203355v, 2012.
Feng, X., Li, Q., Tao, Y., Ding, S., Chen, Y., and Li, X.-D.: Impact of Coal
Replacing Project on atmospheric fine aerosol nitrate loading and formation
pathways in urban Tianjin: Insights from chemical composition and 15N and
18O isotope ratios, Sci. Total Environ., 708, 134797,
https://doi.org/10.1016/j.scitotenv.2019.134797, 2020.
Fountoukis, C. and Nenes, A.: ISORROPIA II: a computationally efficient
thermodynamic equilibrium model for
K+–Ca2+–Mg2+–
Freyer, H. D.: Seasonal variation of
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.
Frost, G. J., McKeen, S. A., Trainer, M., Ryerson, T. B., Neuman, J. A.,
Roberts, J. M., Swanson, A., Holloway, J. S., Sueper, D. T., Fortin, T.,
Parrish, D. D., Fehsenfeld, F. C., Flocke, F., Peckham, S. E., Grell, G. A.,
Kowal, D., Cartwright, J., Auerbach, N., and Habermann, T.: Effects of
changing power plant NOx emissions on ozone in the eastern United
States: Proof of concept, J. Geophys. Res.-Atmos., 111, D12306,
https://doi.org/10.1029/2005JD006354, 2006.
Galloway, J. N., Dentener, F. J., Capone, D. G., Boyer, E. W., Howarth, R.
W., Seitzinger, S. P., Asner, G. P., Cleveland, C., Green, P., and Holland,
E.: Nitrogen cycles: past, present, and future, Biogeochemistry, 70,
153–226, https://doi.org/10.1007/s10533-004-0370-0, 2004.
Geng, L., Alexander, B., Cole-Dai, J., Steig, E. J., Savarino, J., Sofen, E.
D., and Schauer, A. J.: Nitrogen isotopes in ice core nitrate linked to
anthropogenic atmospheric acidity change, P. Natl. Acad. Sci. USA, 111,
5808–5812, https://doi.org/10.1073/pnas.1319441111, 2014.
Granger, J. and Sigman, D. M.: Removal of nitrite with sulfamic acid for
nitrate N and O isotope analysis with the denitrifier method, Rapid. Commun.
Mass. Sp., 23, 3753–3762, https://doi.org/10.1002/rcm.4307, 2009.
Greaver, T. L., Clark, C. M., Compton, J. E., Vallano, D., Talhelm, A. F.,
Weaver, C. P., Band, L. E., Baron, J. S., Davidson, E. A., and Tague, C. L.:
Key ecological responses to nitrogen are altered by climate change, Nat.
Clim. Change, 6, 836–843, https://doi.org/10.1038/nclimate3088, 2016.
Guenther, A. B., Jiang, X., Heald, C. L., Sakulyanontvittaya, T., Duhl, T., Emmons, L. K., and Wang, X.: The Model of Emissions of Gases and Aerosols from Nature version 2.1 (MEGAN2.1): an extended and updated framework for modeling biogenic emissions, Geosci. Model Dev., 5, 1471–1492, https://doi.org/10.5194/gmd-5-1471-2012, 2012.
Hand, J. L., Schichtel, B. A., Malm, W. C., Copeland, S., Molenar, J. V.,
Frank, N., and Pitchford, M.: Widespread reductions in haze across the
United States from the early 1990s through 2011, Atmos. Environ., 94,
671–679, https://doi.org/10.1016/j.atmosenv.2014.05.062, 2014.
Hastings, M. G., Jarvis, J. C., and Steig, E. J.: Anthropogenic Impacts on
Nitrogen Isotopes of Ice-Core Nitrate, Science, 324, 1288–1288,
https://doi.org/10.1126/science.1170510, 2009.
Hastings, M. G., Casciotti, K. L., and Elliott, E. M.: Stable isotopes as
tracers of anthropogenic nitrogen sources, deposition, and impacts,
Elements, 9, 339–344, https://doi.org/10.2113/gselements.9.5.339, 2013.
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.
Hoesly, R. M., Smith, S. J., Feng, L., Klimont, Z., Janssens-Maenhout, G., Pitkanen, T., Seibert, J. J., Vu, L., Andres, R. J., Bolt, R. M., Bond, T. C., Dawidowski, L., Kholod, N., Kurokawa, J.-I., Li, M., Liu, L., Lu, Z., Moura, M. C. P., O'Rourke, P. R., and Zhang, Q.: Historical (1750–2014) anthropogenic emissions of reactive gases and aerosols from the Community Emissions Data System (CEDS), Geosci. Model Dev., 11, 369–408, https://doi.org/10.5194/gmd-11-369-2018, 2018.
Hsu, Y.-K., Holsen, T. M., and Hopke, P. K.: Comparison of hybrid receptor
models to locate PCB sources in Chicago, Atmos. Environ., 37, 545–562,
https://doi.org/10.1016/S1352-2310(02)00886-5, 2003.
Hu, L., Millet, D. B., Baasandorj, M., Griffis, T. J., Turner, P., Helmig,
D., Curtis, A. J., and Hueber, J.: Isoprene emissions and impacts over an
ecological transition region in the US Upper Midwest inferred from tall
tower measurements, J. Geophys. Res.-Atmos., 120, 3553–3571,
https://doi.org/10.1002/2014JD022732, 2015.
Huang, J. and Jaeglé, L.: Wintertime enhancements of sea salt aerosol in polar regions consistent with a sea ice source from blowing snow, Atmos. Chem. Phys., 17, 3699–3712, https://doi.org/10.5194/acp-17-3699-2017, 2017.
Hudman, R. C., Moore, N. E., Mebust, A. K., Martin, R. V., Russell, A. R., Valin, L. C., and Cohen, R. C.: Steps towards a mechanistic model of global soil nitric oxide emissions: implementation and space based-constraints, Atmos. Chem. Phys., 12, 7779–7795, https://doi.org/10.5194/acp-12-7779-2012, 2012.
Jaeglé, L., Steinberger, L., Martin, R. V., and Chance, K.: Global
partitioning of NOx sources using satellite observations: Relative
roles of fossil fuel combustion, biomass burning and soil emissions, Faraday
Discuss., 130, 407–423, https://doi.org/10.1039/b502128f, 2005.
Jaeglé, L., Quinn, P. K., Bates, T. S., Alexander, B., and Lin, J.-T.: Global distribution of sea salt aerosols: new constraints from in situ and remote sensing observations, Atmos. Chem. Phys., 11, 3137–3157, https://doi.org/10.5194/acp-11-3137-2011, 2011.
Jaeglé, L., Shah, V., Thornton, J. A., Lopez-Hilfiker, F. D., Lee, B.
H., McDuffie, E. E., Fibiger, D., Brown, S. S., Veres, P., Sparks, T. L.,
Ebben, C. J., Wooldridge, P. J., Kenagy, H. S., Cohen, R. C., Weinheimer, A.
J., Campos, T. L., Montzka, D. D., Digangi, J. P., Wolfe, G. M., Hanisco,
T., Schroder, J. C., Campuzano-Jost, P., Day, D. A., Jimenez, J. L.,
Sullivan, A. P., Guo, H., and Weber, R. J.: Nitrogen Oxides Emissions,
Chemistry, Deposition, and Export Over the Northeast United States During
the WINTER Aircraft Campaign, J. Geophys. Res.-Atmos., 123, 12368–12393,
https://doi.org/10.1029/2018JD029133, 2018.
Kaiser, J., Hastings, M. G., Houlton, B. Z., Röckmann, 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.
Kim, H., Walters, W. W., Bekker, C., Murray, L. T., and Hastings, M. G.: Nitrate chemistry in the northeast US – Part 2: Oxygen isotopes reveal differences in particulate and gas-phase formation, Atmos. Chem. Phys., 23, 4203–4219, https://doi.org/10.5194/acp-23-4203-2023, 2023.
Li, D. and Wang, X.: Nitrogen isotopic signature of soil-released nitric
oxide (NO) after fertilizer application, Atmos. Environ., 42, 4747–4754,
https://doi.org/10.1016/j.atmosenv.2008.01.042, 2008.
Li, J., Zhang, X., Orlando, J., Tyndall, G., and Michalski, G.: Quantifying the nitrogen isotope effects during photochemical equilibrium between NO and NO2: implications for δ15N in tropospheric reactive nitrogen, Atmos. Chem. Phys., 20, 9805–9819, https://doi.org/10.5194/acp-20-9805-2020, 2020.
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, 118028,
https://doi.org/10.1016/j.atmosenv.2020.118028, 2021.
Li, Z., Walters, W. W., Hastings, M. G., Zhang, Y., Song, L., Liu, D.,
Zhang, W., Pan, Y., Fu, P., and Fang, Y.: Nitrate Isotopic Composition in
Precipitation at a Chinese Megacity: Seasonal Variations, Atmospheric
Processes, and Implications for Sources, Earth Space Sci., 6,
2200–2213, https://doi.org/10.1029/2019EA000759, 2019.
Liu, H., Jacob, D. J., Bey, I., and Yantosca, R. M.: Constraints from 210Pb
and 7Be on wet deposition and transport in a global three-dimensional
chemical tracer model driven by assimilated meteorological fields, J.
Geophys. Res.-Atmos., 106, 12109–12128,
https://doi.org/10.1029/2000JD900839, 2001.
McDuffie, E. E., Smith, S. J., O'Rourke, P., Tibrewal, K., Venkataraman, C., Marais, E. A., Zheng, B., Crippa, M., Brauer, M., and Martin, R. V.: A global anthropogenic emission inventory of atmospheric pollutants from sector- and fuel-specific sources (1970–2017): an application of the Community Emissions Data System (CEDS), Earth Syst. Sci. Data, 12, 3413–3442, https://doi.org/10.5194/essd-12-3413-2020, 2020.
Michalski, G., Scott, Z., Kabiling, M., and Thiemens, M. H.: First
measurements and modeling of Δ17O in atmospheric nitrate, Geophys.
Res. Lett., 30, 1870, https://doi.org/10.1029/2003GL017015, 2003.
Miller, D. J., Wojtal, P. K., Clark, S. C., and Hastings, M. G.: Vehicle NOx
emission plume isotopic signatures: Spatial variability across the eastern
United States, J. Geophys. Res.-Atmos., 122, 2016JD025877,
https://doi.org/10.1002/2016JD025877, 2017.
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, 12–058,
https://doi.org/10.1029/2018GL079619, 2018.
Millet, D. B., Guenther, A., Siegel, D. A., Nelson, N. B., Singh, H. B., de Gouw, J. A., Warneke, C., Williams, J., Eerdekens, G., Sinha, V., Karl, T., Flocke, F., Apel, E., Riemer, D. D., Palmer, P. I., and Barkley, M.: Global atmospheric budget of acetaldehyde: 3-D model analysis and constraints from in-situ and satellite observations, Atmos. Chem. Phys., 10, 3405–3425, https://doi.org/10.5194/acp-10-3405-2010, 2010.
Miyazaki, K., Eskes, H., Sudo, K., Boersma, K. F., Bowman, K., and Kanaya, Y.: Decadal changes in global surface NOx emissions from multi-constituent satellite data assimilation, Atmos. Chem. Phys., 17, 807–837, https://doi.org/10.5194/acp-17-807-2017, 2017.
Murray, L. T.: Lightning NOx and impacts on air quality, Current
Pollution Reports, 2, 115–133, https://doi.org/10.1007/s40726-016-0031-7,
2016.
Murray, L. T., Jacob, D. J., Logan, J. A., Hudman, R. C., and Koshak, W. J.:
Optimized regional and interannual variability of lightning in a global
chemical transport model constrained by LIS/OTD satellite data, J. Geophys.
Res.-Atmos., 117, D20307, https://doi.org/10.1029/2012JD017934, 2012.
Pinder, R. W., Davidson, E. A., Goodale, C. L., Greaver, T. L., Herrick, J.
D., and Liu, L.: Climate change impacts of US reactive nitrogen, P. Natl.
Acad. Sci. USA, 109, 7671–7675, https://doi.org/10.1073/pnas.1114243109, 2012.
Prinn, R. G.: The cleansing capacity of the atmosphere, Annu. Rev. Environ.
Res., 28, 29–57,
https://doi.org/10.1146/annurev.energy.28.011503.163425, 2003.
Pye, H. O. T., Chan, A. W. H., Barkley, M. P., and Seinfeld, J. H.: Global modeling of organic aerosol: the importance of reactive nitrogen (NOx and NO3), Atmos. Chem. Phys., 10, 11261–11276, https://doi.org/10.5194/acp-10-11261-2010, 2010.
Ridley, D. A., Heald, C. L., and Ford, B.: North African dust export and
deposition: A satellite and model perspective, J. Geophys. Res.-Atmos., 117, D02202,
https://doi.org/10.1029/2011JD016794, 2012.
Salamalikis, V., Argiriou, A. A., and Dotsika, E.: Stable isotopic
composition of atmospheric water vapor in Patras, Greece: A concentration
weighted trajectory approach, Atmos. Res., 152, 93–104,
https://doi.org/10.1016/j.atmosres.2014.02.021, 2015.
Savard, M. M., Cole, A., Smirnoff, A., and Vet, R.: δ15N values of
atmospheric N species simultaneously collected using sector-based samplers
distant from sources – Isotopic inheritance and fractionation, Atmos.
Environ., 162, 11–22, https://doi.org/10.1016/j.atmosenv.2017.05.010, 2017.
Savarino, J., Morin, S., Erbland, J., Grannec, F., Patey, M. D., Vicars, W.,
Alexander, B., and Achterberg, E. P.: Isotopic composition of atmospheric
nitrate in a tropical marine boundary layer, P. Natl. Acad. Sci. USA, 110,
17668–17673, https://doi.org/10.1073/pnas.1216639110, 2013.
Sharma, H. D., Jervis, R. E., and Wong, K. Y.: Isotopic exchange reactions
in nitrogen oxides, J. Phys. Chem., 74, 923–933,
https://doi.org/10.1021/j100699a044, 1970.
Sickles II, J. E. and Shadwick, D. S.: Air quality and atmospheric deposition in the eastern US: 20 years of change, Atmos. Chem. Phys., 15, 173–197, https://doi.org/10.5194/acp-15-173-2015, 2015.
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.
Stein, A. F., Draxler, R. R., Rolph, G. D., Stunder, B. J., 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.
U.S. Environmental Protection Agency Clean Air Markets Division Clean Air Status and Trends Network (CASTNET): Filter Pack Concentrations – Weekly, http://www.epa.gov/castnet, last access: 4 March 2022.
van der Werf, G. R., Randerson, J. T., Giglio, L., van Leeuwen, T. T., Chen, Y., Rogers, B. M., Mu, M., van Marle, M. J. E., Morton, D. C., Collatz, G. J., Yokelson, R. J., and Kasibhatla, P. S.: Global fire emissions estimates during 1997–2016, Earth Syst. Sci. Data, 9, 697–720, https://doi.org/10.5194/essd-9-697-2017, 2017.
Vicars, W. C., Morin, S., Savarino, J., Wagner, N. L., Erbland, J., Vince,
E., Martins, J. M. F., Lerner, B. M., Quinn, P. K., Coffman, D. J., and
others: Spatial and diurnal variability in reactive nitrogen oxide chemistry
as reflected in the isotopic composition of atmospheric nitrate: Results
from the CalNex 2010 field study, J. Geophys. Res.-Atmos., 118, 10567–10588,
https://doi.org/10.1002/jgrd.50680, 2013.
Walker, J. M., Philip, S., Martin, R. V., and Seinfeld, J. H.: Simulation of nitrate, sulfate, and ammonium aerosols over the United States, Atmos. Chem. Phys., 12, 11213–11227, https://doi.org/10.5194/acp-12-11213-2012, 2012.
Walker, J. T., Beachley, G., Amos, H. M., Baron, J. S., Bash, J.,
Baumgardner, R., Bell, M. D., Benedict, K. B., Chen, X., and Clow, D. W.:
Toward the improvement of total nitrogen deposition budgets in the United
States, Sci. Total Environ., 691, 1328–1352,
https://doi.org/10.1016/j.scitotenv.2019.07.058, 2019.
Walters, W.: Data for, “Nitrate Chemistry in the Northeast US Part 1 & Part 2”, Harvard Dataverse V1 [data set], https://doi.org/10.7910/DVN/X6BB1I, 2022.
Walters, W. W. and Michalski, G.: Theoretical calculation of nitrogen
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.: Ab initio study of nitrogen and
position-specific oxygen kinetic isotope effects in the NO + O3
reaction, J. Chem. Phys., 145, 224311, https://doi.org/10.1063/1.4968562,
2016a.
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, 2016b.
Walters, W. W., Tharp, B. D., Fang, H., Kozak, B. J., and Michalski, G.:
Nitrogen isotope composition of thermally produced NOx from various
fossil-fuel combustion sources, Environ. Sci. Technol., 49, 11363–11371,
https://doi.org/10.1021/acs.est.5b02769, 2015a.
Walters, W. W., Goodwin, S. R., and Michalski, G.: Nitrogen Stable Isotope
Composition (δ15N) of Vehicle-Emitted NOx, Environ. Sci.
Technol., 49, 2278–2285, https://doi.org/10.1021/es505580v, 2015b.
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, 2015GL066438, https://doi.org/10.1002/2015GL066438, 2016.
Walters, W. W., Fang, H., and Michalski, G.: Summertime diurnal variations
in the isotopic composition of atmospheric nitrogen dioxide at a small
midwestern United States city, Atmos. Environ., 179, 1–11,
https://doi.org/10.1016/j.atmosenv.2018.01.047, 2018.
Wang, X., Jacob, D. J., Downs, W., Zhai, S., Zhu, L., Shah, V., Holmes, C. D., Sherwen, T., Alexander, B., Evans, M. J., Eastham, S. D., Neuman, J. A., Veres, P. R., Koenig, T. K., Volkamer, R., Huey, L. G., Bannan, T. J., Percival, C. J., Lee, B. H., and Thornton, J. A.: Global tropospheric halogen (Cl, Br, I) chemistry and its impact on oxidants, Atmos. Chem. Phys., 21, 13973–13996, https://doi.org/10.5194/acp-21-13973-2021, 2021.
Wesely, M. L. and Lesht, B. M.: Comparison of RADM dry deposition algorithms
with a site-specific method for inferring dry deposition, Water Air
Soil Pollut., 44, 273–293, https://doi.org/10.1007/BF00279259, 1989.
Xing, Y.-F., Xu, Y.-H., Shi, M.-H., and Lian, Y.-X.: The impact of PM2.5 on
the human respiratory system, J. Thorac. Dis., 8, E69–E74,
https://doi.org/10.3978/j.issn.2072-1439.2016.01.19, 2016.
Yu, Z. and Elliott, E. M.: Novel Method for Nitrogen Isotopic Analysis of
Soil-Emitted Nitric Oxide, Environ. Sci. Technol., 51, 6268–6278,
https://doi.org/10.1021/acs.est.7b00592, 2017.
Zhang, R., Tie, X., and Bond, D. W.: Impacts of anthropogenic and natural
NOx sources over the U.S. on tropospheric chemistry, P. Natl. Acad. Sci.,
100, 1505–1509, https://doi.org/10.1073/pnas.252763799, 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
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.
Nitrate is a critical component of the atmosphere that degrades air quality and ecosystem...
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