Articles | Volume 18, issue 9
https://doi.org/10.5194/acp-18-6381-2018
© Author(s) 2018. 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-18-6381-2018
© Author(s) 2018. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
04 May 2018
Research article |
| 04 May 2018
| 04 May 2018
Triple oxygen isotopes indicate urbanization affects sources of nitrate in wet and dry atmospheric deposition
David M. Nelson
CORRESPONDING AUTHOR
University of Maryland Center for Environmental Science,
Appalachian Laboratory, Frostburg, MD 21532, USA
Nagoya University, Graduate School of Environmental Studies, Nagoya,
464-8601, Japan
Urumu Tsunogai
Nagoya University, Graduate School of Environmental Studies, Nagoya,
464-8601, Japan
Dong Ding
Nagoya University, Graduate School of Environmental Studies, Nagoya,
464-8601, Japan
Takuya Ohyama
Nagoya University, Graduate School of Environmental Studies, Nagoya,
464-8601, Japan
Daisuke D. Komatsu
Nagoya University, Graduate School of Environmental Studies, Nagoya,
464-8601, Japan
present address: Tokai University, Department of Marine and Earth
Science, Tokai, Japan
Fumiko Nakagawa
Nagoya University, Graduate School of Environmental Studies, Nagoya,
464-8601, Japan
Izumi Noguchi
Hokkaido Research Organization, Department of Environmental and
Geological Research, Institute of Environmental Sciences, Sapporo, 060-0819,
Japan
Takashi Yamaguchi
Hokkaido Research Organization, Department of Environmental and
Geological Research, Institute of Environmental Sciences, Sapporo, 060-0819,
Japan
Related authors
Joel T. Bostic, David M. Nelson, and Keith N. Eshleman
Biogeosciences, 20, 2485–2498, https://doi.org/10.5194/bg-20-2485-2023, https://doi.org/10.5194/bg-20-2485-2023, 2023
Short summary
Short summary
Land-use changes can affect water quality. We used tracers of pollution sources and water flow paths to show that an urban watershed exports variable sources during storm events relative to a less developed watershed. Our results imply that changing precipitation patterns combined with increasing urbanization may alter sources of pollution in the future.
Matthew L. Trumper, Daniel Griffin, Sarah E. Hobbie, Ian M. Howard, David M. Nelson, Peter B. Reich, and Kendra K. McLauchlan
Biogeosciences, 17, 4509–4522, https://doi.org/10.5194/bg-17-4509-2020, https://doi.org/10.5194/bg-17-4509-2020, 2020
Short summary
Short summary
We developed century-scale records of wood nitrogen isotopes (δ15N) from 16 trees across a long-term savanna fire experiment. Results show similar long-term trajectories in three out of four burn treatments. Lack of evidence to support our hypotheses underscores the complexity of nitrogen dynamics inferred from wood δ15N. This is the first study to our knowledge to investigate multi-decadal effects of fire at different return intervals on wood δ15N, a potential proxy of nitrogen availability.
Weitian Ding, Urumu Tsunogai, and Fumiko Nakagawa
Biogeosciences, 21, 4717–4722, https://doi.org/10.5194/bg-21-4717-2024, https://doi.org/10.5194/bg-21-4717-2024, 2024
Short summary
Short summary
Past studies have used the Δ17O of stream nitrate to estimate the gross nitrification rates (GNRs) in each forested catchment by approximating the Δ17O value of soil nitrate to be equal to that of stream nitrate. Based on inference and calculation of measured data, we found that this approximation resulted in an overestimated GNR. Therefore, it is essential to clarify and verify the Δ17O NO3− values in forested soils and streams before applying the Δ17O values of stream NO3− to GNR estimation.
Joel T. Bostic, David M. Nelson, and Keith N. Eshleman
Biogeosciences, 20, 2485–2498, https://doi.org/10.5194/bg-20-2485-2023, https://doi.org/10.5194/bg-20-2485-2023, 2023
Short summary
Short summary
Land-use changes can affect water quality. We used tracers of pollution sources and water flow paths to show that an urban watershed exports variable sources during storm events relative to a less developed watershed. Our results imply that changing precipitation patterns combined with increasing urbanization may alter sources of pollution in the future.
Weitian Ding, Urumu Tsunogai, Fumiko Nakagawa, Takashi Sambuichi, Masaaki Chiwa, Tamao Kasahara, and Ken'ichi Shinozuka
Biogeosciences, 20, 753–766, https://doi.org/10.5194/bg-20-753-2023, https://doi.org/10.5194/bg-20-753-2023, 2023
Short summary
Short summary
By monitoring the concentration and Δ17O of stream nitrate in three forested streams, the new nitrogen saturation index of forested catchments (Matm/Datm ratio) was estimated. We found that (1) the unprocessed atmospheric nitrate in our studied forested stream (FK1 catchment) was the highest ever reported in forested streams; (2) the Matm/Datm ratio can be used as a robust index for evaluating nitrogen saturation in forested catchments as the Matm/Datm ratio is independent of the precipitation.
Weitian Ding, Urumu Tsunogai, and Fumiko Nakagawa
Biogeosciences Discuss., https://doi.org/10.5194/bg-2022-236, https://doi.org/10.5194/bg-2022-236, 2023
Revised manuscript not accepted
Short summary
Short summary
Past studies used the Δ17O of stream nitrate to estimate GNR in each forested catchment. However, the GNR estimated from the Δ17O of stream nitrate using the equations was more than six times the actual GNR in our simulated calculation for a forested catchment. As a result, it must be essential to clarify/verify the distribution of the Δ17O values of NO3− in forested soils before applying the Δ17O values of stream NO3− to estimate GNR.
Weitian Ding, Urumu Tsunogai, Fumiko Nakagawa, Takashi Sambuichi, Hiroyuki Sase, Masayuki Morohashi, and Hiroki Yotsuyanagi
Biogeosciences, 19, 3247–3261, https://doi.org/10.5194/bg-19-3247-2022, https://doi.org/10.5194/bg-19-3247-2022, 2022
Short summary
Short summary
Excessive leaching of nitrate from forested catchments during storm events degrades water quality and causes eutrophication in downstream areas. Thus, tracing the source of nitrate increase during storm events in forested streams is important for sustainable forest management. Based on the isotopic compositions of stream nitrate, including Δ17O, this study clarifies that the source of stream nitrate increase during storm events was soil nitrate in the riparian zone.
Hao Xu, Urumu Tsunogai, Fumiko Nakagawa, Keiichi Sato, and Hiroshi Tanimoto
Atmos. Chem. Phys. Discuss., https://doi.org/10.5194/acp-2021-1099, https://doi.org/10.5194/acp-2021-1099, 2022
Revised manuscript not accepted
Short summary
Short summary
Using triple oxygen isotopic composition (Δ17O) of ozone as a new tracer, we estimated the absolute concentrations of stratospheric ozone supplied through stratosphere-troposphere transport in the troposphere. We observed the diurnal variations in the Δ17O of ozone, which could have affected studies (field measurements, atmospheric modeling) using Δ17O to constrain atmospheric chemical paths. Our study provides an important basis for a better understanding of ozone behavior in the troposphere.
Matthew L. Trumper, Daniel Griffin, Sarah E. Hobbie, Ian M. Howard, David M. Nelson, Peter B. Reich, and Kendra K. McLauchlan
Biogeosciences, 17, 4509–4522, https://doi.org/10.5194/bg-17-4509-2020, https://doi.org/10.5194/bg-17-4509-2020, 2020
Short summary
Short summary
We developed century-scale records of wood nitrogen isotopes (δ15N) from 16 trees across a long-term savanna fire experiment. Results show similar long-term trajectories in three out of four burn treatments. Lack of evidence to support our hypotheses underscores the complexity of nitrogen dynamics inferred from wood δ15N. This is the first study to our knowledge to investigate multi-decadal effects of fire at different return intervals on wood δ15N, a potential proxy of nitrogen availability.
Fumiko Nakagawa, Urumu Tsunogai, Yusuke Obata, Kenta Ando, Naoyuki Yamashita, Tatsuyoshi Saito, Shigeki Uchiyama, Masayuki Morohashi, and Hiroyuki Sase
Biogeosciences, 15, 7025–7042, https://doi.org/10.5194/bg-15-7025-2018, https://doi.org/10.5194/bg-15-7025-2018, 2018
Short summary
Short summary
To clarify the biological processing of nitrate within temperate forested catchments using unprocessed atmospheric nitrate exported from each catchment as a tracer, we continuously monitored stream nitrate concentrations and stable isotopic compositions in three forested catchments for more than 2 years. We concluded that the export flux of unprocessed atmospheric nitrate relative to the deposition flux in each forest ecosystem is applicable as an index for nitrogen saturation.
Urumu Tsunogai, Takanori Miyauchi, Takuya Ohyama, Daisuke D. Komatsu, Fumiko Nakagawa, Yusuke Obata, Keiichi Sato, and Tsuyoshi Ohizumi
Biogeosciences, 13, 3441–3459, https://doi.org/10.5194/bg-13-3441-2016, https://doi.org/10.5194/bg-13-3441-2016, 2016
Short summary
Short summary
We quantified the influence of changes in land use and population density between each catchment area on the fate of atmospheric nitrate, by determining the areal distribution and seasonal variation in stable isotopic compositions of nitrate for more than 30 streams within a same watershed. We found that the absolute concentrations of atmospheric nitrate were almost the same between the streams irrespective to the changes in land use and population density.
U. Tsunogai, D. D. Komatsu, T. Ohyama, A. Suzuki, F. Nakagawa, I. Noguchi, K. Takagi, M. Nomura, K. Fukuzawa, and H. Shibata
Biogeosciences, 11, 5411–5424, https://doi.org/10.5194/bg-11-5411-2014, https://doi.org/10.5194/bg-11-5411-2014, 2014
F. Nakagawa, A. Suzuki, S. Daita, T. Ohyama, D. D. Komatsu, and U. Tsunogai
Biogeosciences, 10, 3547–3558, https://doi.org/10.5194/bg-10-3547-2013, https://doi.org/10.5194/bg-10-3547-2013, 2013
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 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
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
Short summary
Short summary
A seasonal analysis of the nitrogen isotopes of atmospheric nitrate over the remote Southern Ocean reveals that similar natural NOx sources dominate in spring and summer, while winter is representative of background-level conditions. The oxygen isotopes suggest that similar oxidation pathways involving more ozone occur in spring and winter, while the hydroxyl radical is the main oxidant in summer. This work helps to constrain NOx cycling and oxidant budgets in a data-sparse remote marine region.
Claire Bekker, Wendell W. Walters, Lee T. Murray, and Meredith G. Hastings
Atmos. Chem. Phys., 23, 4185–4201, https://doi.org/10.5194/acp-23-4185-2023, https://doi.org/10.5194/acp-23-4185-2023, 2023
Short summary
Short summary
Nitrate is a critical component of the atmosphere that degrades air quality and ecosystem health. We have investigated the nitrogen isotope compositions of nitrate from deposition samples collected across the northeastern United States. Spatiotemporal variability in the nitrogen isotope compositions was found to track with nitrate formation chemistry. Our results highlight that nitrogen isotope compositions may be a robust tool for improving model representation of nitrate chemistry.
Heejeong Kim, Wendell W. Walters, Claire Bekker, Lee T. Murray, and Meredith G. Hastings
Atmos. Chem. Phys., 23, 4203–4219, https://doi.org/10.5194/acp-23-4203-2023, https://doi.org/10.5194/acp-23-4203-2023, 2023
Short summary
Short summary
Atmospheric nitrate has an important impact on human and ecosystem health. We evaluated atmospheric nitrate formation pathways in the northeastern US utilizing oxygen isotope compositions, which indicated a significant difference between the phases of nitrate (i.e., gas vs. particle). Comparing the observations with model simulations indicated that N2O5 hydrolysis chemistry was overpredicted. Our study has important implications for improving atmospheric chemistry model representation.
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
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
Aikawa, M., Ohara, T., Hiraki, T., Oishi, O., Tsuji, A., Yamagami, M., Murano, K., and Mukai, H.: Significant geographic gradients in particulate sulfate over Japan determined from multiple-site measurements and a chemical transport model: Impacts of transboundary pollution from the Asian continent, Atmos. Environ., 44, 381–391, https://doi.org/10.1016/j.atmosenv.2009.10.025, 2010.
Akimoto, H.: Global air quality and pollution, Science, 302, 1716–1719, https://doi.org/10.1126/science.1092666, 2003.
Alexander, B., Hastings, M. G., Allman, D. J., Dachs, J., Thornton, J. A., and Kunasek, S. A.: Quantifying atmospheric nitrate formation pathways based on a global model of the oxygen isotopic composition (Δ17O) of atmospheric nitrate, Atmos. Chem. Phys., 9, 5043–5056, https://doi.org/10.5194/acp-9-5043-2009, 2009.
Balestrini, R., Galli, L., and Tartari, G.: Wet and dry atmospheric deposition at prealpine and alpine sites in northern Italy, Atmos. Environ., 34, 1455–1470, https://doi.org/10.1016/S1352-2310(99)00404-5, 2000.
Ban, S., Matsuda, K., Sato, K., and Ohizumi, T.: Long-term assessment of nitrogen deposition at remote EANET sites in Japan, Atmos. Environ., 146, 70–78, https://doi.org/10.1016/j.atmosenv.2016.04.015, 2016.
Bloom, D. E., Canning, D., and Fink, G.: Urbanization and the wealth of nations, Science, 319, 772–775, https://doi.org/10.1126/science.1153057, 2008.
Brown, S. S., Ryerson, T. B., Wollny, A. G., Brock, C. A., Peltier, R., Sullivan, A. P., Weber, R. J., Dube, W. P., Trainer, M., Meagher, J. F., Fehsenfeld, F. C., and Ravishankara, A. R.: Variability in nocturnal nitrogen oxide processing and its role in regional air quality, Science, 311, 67–70, https://doi.org/10.1126/science.1120120, 2006.
Carslaw, N., Creasey, D. J., Heard, D. E., Jacobs, P. J., Lee, J. D., Lewis, A. C., McQuaid, J. B., Pilling, M. J., Bauguitte, S., Penkett, S. A., Monks, P. S., and Salisbury, G.: Eastern Atlantic Spring Experiment 1997 (EASE97) – 2. Comparisons of model concentrations of OH, HO2, and RO2 with measurements, J. Geophys. Res.-Atmos., 107, 4190, https://doi.org/10.1029/2001jd001568, 2002.
Casciotti, K. L., Bohlke, J. K., McIlvin, M. R., Mroczkowski, S. J., and Hannon, J. E.: Oxygen isotopes in nitrite: Analysis, calibration, and equilibration, Anal. Chem., 79, 2427–2436, https://doi.org/10.1021/ac061598h, 2007.
Celle-Jeanton, H., Travi, Y., Loye-Pilot, M. D., Huneau, F., and Bertrand, G.: Rainwater chemistry at a Mediterranean inland station (Avignon, France): Local contribution versus long-range supply, Atmos. Res., 91, 118–126, https://doi.org/10.1016/j.atmosres.2008.06.003, 2009.
Crutzen, P. J.: Role of NO and NO2 in the chemistry of the troposphere and stratosphere, Annu. Rev. Earth Pl. Sc., 7, 443–472, https://doi.org/10.1146/annurev.ea.07.050179.002303, 1979.
Cumming, G. S., Buerkert, A., Hoffmann, E. M., Schlecht, E., von Cramon-Taubadel, S., and Tscharntke, T.: Implications of agricultural transitions and urbanization for ecosystem services, Nature, 515, 50–57, https://doi.org/10.1038/nature13945, 2014.
Dasch, J. M. and Cadle, S. H.: Wet and dry deposition monitoring in southeastern Michigan, Atmos. Environ., 19, 789–796, https://doi.org/10.1016/0004-6981(85)90067-8, 1985.
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.-Biogeol., 114, G04020, https://doi.org/10.1029/2008JG000889, 2009.
Endo, T., Yagoh, H., Sato, K., Matsuda, K., Hayashi, K., Noguchi, I., and Sawada, K.: Regional characteristics of dry deposition of sulfur and nitrogen compounds at EANET sites in Japan from 2003 to 2008, Atmos. Environ., 45, 1259–1267, https://doi.org/10.1016/j.atmosenv.2010.12.003, 2011.
Erisman, J. W., Draaijers, G., Duyzer, J., Hofschreuder, P., VanLeeuwen, N., Romer, F., Ruijgrok, W., Wyers, P., and Gallagher, M.: Particle deposition to forests – Summary of results and application, Atmos. Environ., 31, 321–332, https://doi.org/10.1016/S1352-2310(96)00223-3, 1997.
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.
Fraser, M. P., Cass, G. R., and Simoneit, B. R. T.: Gas-phase and particle-phase organic compounds emitted from motor vehicle traffic in a Los Angeles roadway tunnel, Environ. Sci. Technol. 32, 2051–2060, https://doi.org/10.1021/es970916e, 1998.
Freyer, H. D.: Seasonal variation of 15N ∕ 14N ratios in atmospheric nitrate species, Tellus B, 43, 30–44, https://doi.org/10.1034/j.1600-0889.1991.00003.x, 1991.
Freyer, H. D., Kley, D., Volzthomas, A., and Kobel, K.: On the interaction of isotopic exchange processes with photochemical reactions in atmospheric oxides of nitrogen, J. Geophys. Res.-Atmos., 98, 14791–14796, https://doi.org/10.1029/93jd00874, 1993.
Galloway, J. N., Dentener, F. J., Capone, D. G., Boyer, E. W., Howarth, R. W., Seitzinger, S. P., Asner, G. P., Cleveland, C. C., Green, P. A., Holland, E. A., Karl, D. M., Michaels, A. F., Porter, J. H., Townsend, A. R., and Vorosmarty, C. J.: Nitrogen cycles: past, present, and future, Biogeochemistry, 70, 153–226, 2004.
Geng, L., Murray, L. T., Mickley, L. J., Lin, P., Fu, Q., Schauer, A. J., and Alexander, B.: Isotopic evidence of multiple controls on atmospheric oxidants over climate transitions, Nature, 546, 133–136, https://doi.org/10.1038/nature22340, 2017.
Guerrieri, R., Vanguelova, E. I., Michalski, G., Heaton, T. H. E., and Mencuccini, M.: Isotopic evidence for the occurrence of biological nitrification and nitrogen deposition processing in forest canopies, Glob. Change Biol., 21, 4613–4626, https://doi.org/10.1111/gcb.13018, 2015.
Guha, T., Lin, C. T., Bhattacharya, S. K., Mahajan, A. S., Ou-Yang, C.-F., Lan, Y.-P., Hsu, S. C., and Liang, M.-C.: Isotopic ratios of nitrate in aerosol samples from Mt. Lulin, a high-altitude station in Central Taiwan, Atmos. Environ., 154, 53–69, 2017.
Gurjar, B. R., Ravindra, K., and Nagpure, A. S.: Air pollution trends over Indian megacities and their local-to-global implications, Atmos. Environ., 142, 475–495, https://doi.org/10.1016/j.atmosenv.2016.06.030, 2016.
Hammer, Ø., Harper, D. A. T., and Ryan, P. D.: PAST: Paleontological statistics software package for education and data analysis, Palaeontol. Electron., 4, 9 pp., 2001.
Hicks, B. B.: Measuring dry deposition: A reassessment of the state-of-the-art, Water Air Soil Poll., 30, 75–90, https://doi.org/10.1007/Bf00305177, 1986.
Hirota, A., Tsunogai, U., Komatsu, D. D., and Nakagawa, F.: Simultaneous determination of δ15N and δ18O of N2O and δ13C of CH4 in nanomolar quantities from a single water sample, Rapid Commun. Mass Sp., 24, 1085–1092, https://doi.org/10.1002/rcm.4483, 2010.
Holtgrieve, G. W., Schindler, D. E., Hobbs, W. O., Leavitt, P. R., Ward, E. J., Bunting, L., Chen, G. J., Finney, B. P., Gregory-Eaves, I., Holmgren, S., Lisac, M. J., Lisi, P. J., Nydick, K., Rogers, L. A., Saros, J. E., Selbie, D. T., Shapley, M. D., Walsh, P. B., and Wolfe, A. P.: A coherent signature of anthropogenic nitrogen deposition to remote watersheds of the Northern hemisphere, Science, 334, 1545–1548, 2011.
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, 2007.
Kaneyasu, N., Ohta, S., and Murao, N.: Seasonal variation in the chemical composition of atmospheric aerosols and gaseous species in Sapporo, Japan, Atmos. Environ., 29, 1559–1568, https://doi.org/10.1016/1352-2310(94)00356-P, 1995.
Kendall, C., Elliott, E. M., and Wankel, S. D.: Tracing anthropogenic input of nitrogen to ecosytems, in: Stable Isotopes in Ecology and Environmental Science, edited by: Michener, R. H., and Lajtha, L. J., Blackwell, Oxford, 375–449, 2007.
Komatsu, D. D., Ishimura, T., Nakagawa, F., and Tsunogai, U.: Determination of the 15N ∕ 14N, 17O ∕ 16O, and 18O ∕ 16O ratios of nitrous oxide by using continuous-flow isotope-ratio mass spectrometry, Rapid Commun. Mass Sp., 22, 1587–1596, 2008.
Li, Y., Schichtel, B. A., Walker, J. T., Schwede, D. B., Chen, X., Lehmann, C. M. B., Puchalski, M. A., Gay, D. A., and Collett, J. L.: Increasing importance of deposition of reduced nitrogen in the United States, P. Natl. Acad. Sci. USA, 113, 5874–5879, https://doi.org/10.1073/pnas.1525736113, 2016.
Lin, M. Y., Horowitz, L. W., Payton, R., Fiore, A. M., and Tonnesen, G.: US surface ozone trends and extremes from 1980 to 2014: Quantifying the roles of rising Asian emissions, domestic controls, wildfires, and climate, Atmos. Chem. Phys., 17, 2943–2970, https://doi.org/10.5194/acp-17-2943-2017, 2017.
Liu, F., Zhang, Q., Ronald, J. V., Zheng, B., Tong, D., Yan, L., Zheng, Y. X., and He, K. B.: Recent reduction in NOx emissions over China: synthesis of satellite observations and emission inventories, Environ. Res. Lett., 11, 114002, https://doi.org/10.1088/1748-9326/11/11/114002, 2016.
McIlvin, M. R. and Altabet, M. A.: Chemical conversion of nitrate and nitrite to nitrous oxide for nitrogen and oxygen isotopic analysis in freshwater and seawater, Anal. Chem., 77, 5589–5595, https://doi.org/10.1021/ac050528s, 2005.
Mehlmann, A. and Warneck, P.: Atmospheric gaseous HNO3 particulate nitrate, and aerosol-size distributions of major ionic species at a rural site in western Germany, Atmos. Environ., 29, 2359–2373, https://doi.org/10.1016/1352-2310(95)00056-5, 1995.
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.
Michalski, G., Meixner, T., Fenn, M., Hernandez, L., Sirulnik, A., Allen, E., and Thiemens, M.: Tracing atmospheric nitrate deposition in a complex semiarid ecosystem using Δ17O, Environ. Sci. Technol., 38, 2175–2181, 2004.
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 Verlag, Berlin, 613–635, 2011.
Monks, P. S.: Gas-phase radical chemistry in the troposphere, Chem. Soc. Rev., 34, 376–395, https://doi.org/10.1039/b307982c, 2005.
Morin, S., Savarino, J., Frey, M. M., Yan, N., Bekki, S., Bottenheim, J. W., and Martins, J. M. F.: Tracing the origin and fate of NOx in the Arctic atmosphere using stable isotopes in nitrate, Science, 322, 730–732, https://doi.org/10.1126/science.1161910, 2008.
Morin, S., 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.
Noguchi, I., Aosier, B., Takada, M., Hamahara, K., Takahashi, H., and Tamada, K.: Developing NDVI Estimation Model of Forest Area in Japan, using Temperature data, Report of Institute of Environmental Sciences, 43–56, 2006.
Noguchi, I., Yamaguchi, T., Sakai, S., and Tsunogai, U.: Comparison of air pollutant measurements by weekly, biweekly, and monthly filter-pack method, Proceedings of the 50th Annual meeting of Japan Society for Atmospheric Environment, 16–18 September 2009, Keio University Hiyoshi Campus, Yokohama, Japan 2009.
Noguchi, I., Yamaguchi, T., Kawamura, M., Matsumoto, R., and Matsuda, K.: Updated program file for dry deposition velocity, Report of Institute of Environmental Sciences, 21–31, 2011.
Redling, K., Elliott, E., Bain, D., and Sherwell, J.: Highway contributions to reactive nitrogen deposition: tracing the fate of vehicular NOx using stable isotopes and plant biomonitors, Biogeochemistry, 116, 261–274, https://doi.org/10.1007/s10533-013-9857-x, 2013.
Riha, K. M., Michalski, G., Gallo, E. L., Lohse, K. A., Brooks, P. D., and Meixner, T.: High atmospheric nitrate inputs and nitrogen turnover in semi-arid urban catchments, Ecosystems, 17, 1309–1325, 2015.
Sabo, R. D., Nelson, D. M., and Eshleman, K. N.: Episodic, seasonal, and annual export of atmospheric and microbial nitrate from a temperate forest, Geophys. Res. Lett., 43, 683–691, https://doi.org/10.1002/2015gl066758, 2016.
Saito, S., Nagao, I., and Tanaka, H.: Relationship of NOx and NMHC to photochemical O3 production in a coastal and metropolitan areas of Japan, Atmos. Environ., 36, 1277–1286, https://doi.org/10.1016/S1352-2310(01)00557-X, 2002.
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.
Skyllakou, K., Murphy, B. N., Megaritis, A. G., Fountoukis, C., and Pandis, S. N.: Contributions of local and regional sources to fine PM in the megacity of Paris, Atmos. Chem. Phys., 14, 2343–2352, https://doi.org/10.5194/acp-14-2343-2014, 2014.
Sofen, E. D., Alexander, B., Steig, E. J., Thiemens, M. H., Kunasek, S. A., Amos, H. M., Schauer, A. J., Hastings, M. G., Bautista, J., Jackson, T. L., Vogel, L. E., McConnell, J. R., Pasteris, D. R., and Saltzman, E. S.: 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, Atmos. Chem. Phys., 14, 5749–5769, https://doi.org/10.5194/acp-14-5749-2014, 2014.
Tørseth, K., Hanssen, J. E., and Semb, A.: Temporal and spatial variations of airborne Mg, Cl, Na, Ca and K in rural areas of Norway, Sci. Total Environ., 234, 75–85, https://doi.org/10.1016/S0048-9697(99)00261-2, 1999.
Tsunogai, U., Kido, T., Hirota, A., Ohkubo, S. B., Komatsu, D. D., and Nakagawa, F.: Sensitive determinations of stable nitrogen isotopic composition of organic nitrogen through chemical conversion into N2O, Rapid Commun. Mass Sp., 22, 345–354, https://doi.org/10.1002/rcm.3368, 2008.
Tsunogai, U., Komatsu, D. D., Daita, S., Kazemi, G. A., Nakagawa, F., Noguchi, I., and Zhang, J.: Tracing the fate of atmospheric nitrate deposited onto a forest ecosystem in Eastern Asia using Δ17O, Atmos. Chem. Phys., 10, 1809–1820, https://doi.org/10.5194/acp-10-1809-2010, 2010.
Tsunogai, U., Miyauchi, T., Ohyama, T., Komatsu, D. D., Nakagawa, F., Obata, Y., Sato, K., and Ohizumi, T.: Accurate and precise quantification of atmospheric nitrate in streams draining land of various uses by using triple oxygen isotopes as tracers, Biogeosciences, 13, 3441–3459, https://doi.org/10.5194/bg-13-3441-2016, 2016.
United Nations: World Urbanization Prospects, the 2014 Revision, United Nations, Population Division, Department of Economic and Social Affairs, New York, 32 pp., 2014.
Uno, I., Wakamatsu, S., and Ueda, H.: Behavior of nocturnal urban boundary layer and air pollutants, J. Jpn. Soc. Air Poll., 23, 102–114, 1988.
Uno, I., Ohara, T., and Wakamatsu, S.: Analysis of wintertime NO2 pollution in the Tokyo Metropolitan area, Atmos. Environ., 30, 703–713, https://doi.org/10.1016/1352-2310(95)00177-8, 1996.
Uno, I., Uematsu, M., Hara, Y., He, Y. J., Ohara, T., Mori, A., Kamaya, T., Murano, K., Sadanaga, Y., and Bandow, H.: Numerical study of the atmospheric input of anthropogenic total nitrate to the marginal seas in the western North Pacific region, Geophys. Res. Lett., 34, L17817, https://doi.org/10.1029/2007gl030338, 2007.
von Glasow, R., Jickells, T. D., Baklanov, A., Carmichael, G. R., Church, T. M., Gallardo, L., Hughes, C., Kanakidou, M., Liss, P. S., Mee, L., Raine, R., Ramachandran, P., Ramesh, R., Sundseth, K., Tsunogai, U., Uematsu, M., and Zhu, T.: Megacities and large urban agglomerations in the coastal zone: Interactions between atmosphere, land, and marine ecosystems, Ambio, 42, 13–28, https://doi.org/10.1007/s13280-012-0343-9, 2013.
Wagstrom, K. M. and Pandis, S. N.: Contribution of long range transport to local fine particulate matter concerns, Atmos. Environ., 45, 2730–2735, https://doi.org/10.1016/j.atmosenv.2011.02.040, 2011.
Walcek, C. J., Brost, R. A., Chang, J. S., and Wesely, M. L.: SO2, sulfate and HNO3 deposition velocities computed using regional landuse and meteorological data, Atmos. Environ., 20, 949–964, https://doi.org/10.1016/0004-6981(86)90279-9, 1986.
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.: 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., 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, 2015.
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.
Wesely, M. L.: Parameterization of surface resistances to gaseous dry deposition in regional-scale numerical models, Atmos. Environ., 23, 1293–1304, https://doi.org/10.1016/0004-6981(89)90153-4, 1989.
Zhang, L., Brook, J. R., and Vet, R.: A revised parameterization for gaseous dry deposition in air-quality models, Atmos. Chem. Phys., 3, 2067–2082, https://doi.org/10.5194/acp-3-2067-2003, 2003.
Zhao, Y., Qiu, L. P., Xu, R. Y., Xie, F. J., Zhang, Q., Yu, Y. Y., Nielsen, C. P., Qin, H. X., Wang, H. K., Wu, X. C., Li, W. Q., and Zhang, J.: Advantages of a city-scale emission inventory for urban air quality research and policy: the case of Nanjing, a typical industrial city in the Yangtze River Delta, China, Atmos. Chem. Phys., 15, 12623–12644, https://doi.org/10.5194/acp-15-12623-2015, 2015.
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.
Atmospheric nitrate may be produced locally and/or come from upwind regions. To address this...
Altmetrics
Final-revised paper
Preprint