Articles | Volume 23, issue 7
https://doi.org/10.5194/acp-23-4203-2023
© 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-23-4203-2023
© Author(s) 2023. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Nitrate chemistry in the northeast US – Part 2: Oxygen isotopes reveal differences in particulate and gas-phase formation
Heejeong Kim
CORRESPONDING AUTHOR
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
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
Claire Bekker
Department of Earth, Environmental, and Planetary Sciences, Brown
University, Providence, RI 02912, USA
now at: Environmental Health Sciences, University of California Los
Angeles, Los Angeles, CA 90095, 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
Related authors
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William J. Collins, Fiona M. O'Connor, Rachael E. Byrom, Øivind Hodnebrog, Patrick Jöckel, Mariano Mertens, Gunnar Myhre, Matthias Nützel, Dirk Olivié, Ragnhild Bieltvedt Skeie, Laura Stecher, Larry W. Horowitz, Vaishali Naik, Gregory Faluvegi, Ulas Im, Lee T. Murray, Drew Shindell, Kostas Tsigaridis, Nathan Luke Abraham, and James Keeble
Atmos. Chem. Phys., 25, 9031–9060, https://doi.org/10.5194/acp-25-9031-2025, https://doi.org/10.5194/acp-25-9031-2025, 2025
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We used 7 climate models that include atmospheric chemistry and find that in a scenario with weak controls on air quality, the warming effects (over 2015 to 2050) of decreases in ozone-depleting substances and increases in air quality pollutants are approximately equal and would make ozone the second highest contributor to warming over this period. We find that for stratospheric ozone recovery, the standard measure of climate effects underestimates a more comprehensive measure.
Paul T. Griffiths, Laura J. Wilcox, Robert J. Allen, Vaishali Naik, Fiona M. O'Connor, Michael Prather, Alex Archibald, Florence Brown, Makoto Deushi, William Collins, Stephanie Fiedler, Naga Oshima, Lee T. Murray, Bjørn H. Samset, Chris Smith, Steven Turnock, Duncan Watson-Parris, and Paul J. Young
Atmos. Chem. Phys., 25, 8289–8328, https://doi.org/10.5194/acp-25-8289-2025, https://doi.org/10.5194/acp-25-8289-2025, 2025
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The Aerosol Chemistry Model Intercomparison Project (AerChemMIP) aimed to quantify the climate and air quality impacts of aerosols and chemically reactive gases. We review its contribution to AR6 (Sixth Assessment Report of the Intergovernmental Panel on Climate Change) and the wider understanding of the role of these species in climate and climate change. We identify challenges and provide recommendations to improve the utility and uptake of climate model data, detailed summary tables of CMIP6 models, experiments, and emergent diagnostics.
Huan Fang and Wendell Walters
EGUsphere, https://doi.org/10.5194/egusphere-2025-923, https://doi.org/10.5194/egusphere-2025-923, 2025
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The Sulfur Tracking Mechanism in CMAQ was used to model the oxygen isotope anomaly (Δ17O) of aerosol sulfate (ASO4) for the first time. This approach allows for a qualitative analysis of sulfate (SO42-) formation processes and comparison with corresponding measurements.
Alexandra M. Catena, Mackenzie L. Smith, Lee T. Murray, Eric M. Leibensperger, Jie Zhang, Margaret J. Schwab, and James J. Schwab
Earth Syst. Sci. Data Discuss., https://doi.org/10.5194/essd-2025-135, https://doi.org/10.5194/essd-2025-135, 2025
Revised manuscript accepted for ESSD
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Methane and carbon dioxide emission rates were calculated for facilities across several sectors in New York State using aerial observations. Of the sampled facilities, landfills dominated the methane emission rates while combustion facilities had the highest carbon dioxide emission rates, followed by landfills. The self-reported EPA inventory is mostly underestimating landfill methane emissions apart from a few facilities with comparable numbers.
Wendell W. Walters, Masayuki Takeuchi, Danielle E. Blum, Gamze Eris, David Tanner, Weiqi Xu, Jean Rivera-Rios, Fobang Liu, Tianchang Xu, Greg Huey, Justin B. Min, Rodney Weber, Nga L. Ng, and Meredith G. Hastings
EGUsphere, https://doi.org/10.5194/egusphere-2024-3860, https://doi.org/10.5194/egusphere-2024-3860, 2024
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We studied how chemicals released from plants and pollution interact in the atmosphere, affecting air quality and climate. By combining laboratory experiments and chemistry models, we tracked unique chemical fingerprints to understand how nitrogen compounds transform to form particles in the air. Our findings help explain the role of these reactions in pollution and provide tools to improve predictions for cleaner air and better climate policies.
Benjamin Hmiel, Vasilii V. Petrenko, Christo Buizert, Andrew M. Smith, Michael N. Dyonisius, Philip Place, Bin Yang, Quan Hua, Ross Beaudette, Jeffrey P. Severinghaus, Christina Harth, Ray F. Weiss, Lindsey Davidge, Melisa Diaz, Matthew Pacicco, James A. Menking, Michael Kalk, Xavier Faïn, Alden Adolph, Isaac Vimont, and Lee T. Murray
The Cryosphere, 18, 3363–3382, https://doi.org/10.5194/tc-18-3363-2024, https://doi.org/10.5194/tc-18-3363-2024, 2024
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The main aim of this research is to improve understanding of carbon-14 that is produced by cosmic rays in ice sheets. Measurements of carbon-14 in ice cores can provide a range of useful information (age of ice, past atmospheric chemistry, past cosmic ray intensity). Our results show that almost all (>99 %) of carbon-14 that is produced in the upper layer of ice sheets is rapidly lost to the atmosphere. Our results also provide better estimates of carbon-14 production rates in deeper ice.
Wendell W. Walters, Masayuki Takeuchi, Nga L. Ng, and Meredith G. Hastings
Geosci. Model Dev., 17, 4673–4687, https://doi.org/10.5194/gmd-17-4673-2024, https://doi.org/10.5194/gmd-17-4673-2024, 2024
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The study introduces a novel chemical mechanism for explicitly tracking oxygen isotope transfer in oxidized reactive nitrogen and odd oxygen using the Regional Atmospheric Chemistry Mechanism, version 2. This model enhances our ability to simulate and compare oxygen isotope compositions of reactive nitrogen, revealing insights into oxidation chemistry. The approach shows promise for improving atmospheric chemistry models and tropospheric oxidation capacity predictions.
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.
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
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Nitrate is a critical component of the atmosphere that degrades air quality and ecosystem health. We have investigated the nitrogen isotope compositions of nitrate from deposition samples collected across the northeastern United States. Spatiotemporal variability in the nitrogen isotope compositions was found to track with nitrate formation chemistry. Our results highlight that nitrogen isotope compositions may be a robust tool for improving model representation of nitrate chemistry.
Róisín Commane, Andrew Hallward-Driemeier, and Lee T. Murray
Atmos. Meas. Tech., 16, 1431–1441, https://doi.org/10.5194/amt-16-1431-2023, https://doi.org/10.5194/amt-16-1431-2023, 2023
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Methane / ethane ratios can be used to identify and partition the different sources of methane, especially in areas with natural gas mixed with biogenic methane emissions, such as cities. We tested three commercially available laser-based analyzers for sensitivity, precision, size, power requirement, ease of use on mobile platforms, and expertise needed to operate the instrument, and we make recommendations for use in various situations.
Hao Guo, Clare M. Flynn, Michael J. Prather, Sarah A. Strode, Stephen D. Steenrod, Louisa Emmons, Forrest Lacey, Jean-Francois Lamarque, Arlene M. Fiore, Gus Correa, Lee T. Murray, Glenn M. Wolfe, Jason M. St. Clair, Michelle Kim, John Crounse, Glenn Diskin, Joshua DiGangi, Bruce C. Daube, Roisin Commane, Kathryn McKain, Jeff Peischl, Thomas B. Ryerson, Chelsea Thompson, Thomas F. Hanisco, Donald Blake, Nicola J. Blake, Eric C. Apel, Rebecca S. Hornbrook, James W. Elkins, Eric J. Hintsa, Fred L. Moore, and Steven C. Wofsy
Atmos. Chem. Phys., 23, 99–117, https://doi.org/10.5194/acp-23-99-2023, https://doi.org/10.5194/acp-23-99-2023, 2023
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We have prepared a unique and unusual result from the recent ATom aircraft mission: a measurement-based derivation of the production and loss rates of ozone and methane over the ocean basins. These are the key products of chemistry models used in assessments but have thus far lacked observational metrics. It also shows the scales of variability of atmospheric chemical rates and provides a major challenge to the atmospheric models.
Wendell W. Walters, Madeline Karod, Emma Willcocks, Bok H. Baek, Danielle E. Blum, and Meredith G. Hastings
Atmos. Chem. Phys., 22, 13431–13448, https://doi.org/10.5194/acp-22-13431-2022, https://doi.org/10.5194/acp-22-13431-2022, 2022
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Atmospheric ammonia and its products are a significant source of urban haze and nitrogen deposition. We have investigated the seasonal source contributions to a mid-sized city in the northeastern US megalopolis utilizing geospatial statistical analysis and novel isotopic constraints, which indicate that vehicle emissions were significant components of the urban-reduced nitrogen budget. Reducing vehicle ammonia emissions should be considered to improve ecosystems and human health.
Jessica M. Burger, Julie Granger, Emily Joyce, Meredith G. Hastings, Kurt A. M. Spence, and Katye E. Altieri
Atmos. Chem. Phys., 22, 1081–1096, https://doi.org/10.5194/acp-22-1081-2022, https://doi.org/10.5194/acp-22-1081-2022, 2022
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The nitrogen (N) isotopic composition of atmospheric nitrate in the Southern Ocean (SO) marine boundary layer (MBL) reveals the importance of oceanic alkyl nitrate emissions as a source of reactive N to the atmosphere. The oxygen isotopic composition suggests peroxy radicals contribute up to 63 % to NO oxidation and that nitrate forms via the OH pathway. This work improves our understanding of reactive N sources and cycling in a remote marine region, a proxy for the pre-industrial atmosphere.
Liam Bindle, Randall V. Martin, Matthew J. Cooper, Elizabeth W. Lundgren, Sebastian D. Eastham, Benjamin M. Auer, Thomas L. Clune, Hongjian Weng, Jintai Lin, Lee T. Murray, Jun Meng, Christoph A. Keller, William M. Putman, Steven Pawson, and Daniel J. Jacob
Geosci. Model Dev., 14, 5977–5997, https://doi.org/10.5194/gmd-14-5977-2021, https://doi.org/10.5194/gmd-14-5977-2021, 2021
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Atmospheric chemistry models like GEOS-Chem are versatile tools widely used in air pollution and climate studies. The simulations used in such studies can be very computationally demanding, and thus it is useful if the model can simulate a specific geographic region at a higher resolution than the rest of the globe. Here, we implement, test, and demonstrate a new variable-resolution capability in GEOS-Chem that is suitable for simulations conducted on supercomputers.
Lee T. Murray, Eric M. Leibensperger, Clara Orbe, Loretta J. Mickley, and Melissa Sulprizio
Geosci. Model Dev., 14, 5789–5823, https://doi.org/10.5194/gmd-14-5789-2021, https://doi.org/10.5194/gmd-14-5789-2021, 2021
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Chemical-transport models are tools used to study air pollution and inform public policy. However, they are limited by the availability of archived meteorology. Here, we describe how the GEOS-Chem chemical-transport model may now be driven by meteorology archived from a state-of-the-art general circulation model for past and future climates, allowing it to be used to explore the impact of climate change on air pollution and atmospheric composition.
Hao Guo, Clare M. Flynn, Michael J. Prather, Sarah A. Strode, Stephen D. Steenrod, Louisa Emmons, Forrest Lacey, Jean-Francois Lamarque, Arlene M. Fiore, Gus Correa, Lee T. Murray, Glenn M. Wolfe, Jason M. St. Clair, Michelle Kim, John Crounse, Glenn Diskin, Joshua DiGangi, Bruce C. Daube, Roisin Commane, Kathryn McKain, Jeff Peischl, Thomas B. Ryerson, Chelsea Thompson, Thomas F. Hanisco, Donald Blake, Nicola J. Blake, Eric C. Apel, Rebecca S. Hornbrook, James W. Elkins, Eric J. Hintsa, Fred L. Moore, and Steven Wofsy
Atmos. Chem. Phys., 21, 13729–13746, https://doi.org/10.5194/acp-21-13729-2021, https://doi.org/10.5194/acp-21-13729-2021, 2021
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The NASA Atmospheric Tomography (ATom) mission built a climatology of the chemical composition of tropospheric air parcels throughout the middle of the Pacific and Atlantic oceans. The level of detail allows us to reconstruct the photochemical budgets of O3 and CH4 over these vast, remote regions. We find that most of the chemical heterogeneity is captured at the resolution used in current global chemistry models and that the majority of reactivity occurs in the
hottest20 % of parcels.
Jiajue Chai, Jack E. Dibb, Bruce E. Anderson, Claire Bekker, Danielle E. Blum, Eric Heim, Carolyn E. Jordan, Emily E. Joyce, Jackson H. Kaspari, Hannah Munro, Wendell W. Walters, and Meredith G. Hastings
Atmos. Chem. Phys., 21, 13077–13098, https://doi.org/10.5194/acp-21-13077-2021, https://doi.org/10.5194/acp-21-13077-2021, 2021
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Nitrous acid (HONO) derived from wildfire emissions plays a key role in controlling atmospheric oxidation chemistry. However, the HONO budget remains poorly constrained. By combining the field-observed concentrations and novel isotopic composition (N and O) of HONO and nitrogen oxides (NOx), we quantitatively constrained the relative contribution of each pathway to secondary HONO production and the relative importance of major atmospheric oxidants (ozone versus peroxy) in aged wildfire smoke.
Huan Fang, Wendell W. Walters, David Mase, and Greg Michalski
Geosci. Model Dev., 14, 5001–5022, https://doi.org/10.5194/gmd-14-5001-2021, https://doi.org/10.5194/gmd-14-5001-2021, 2021
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A new photochemical reaction scheme that incorporates nitrogen isotopes has been developed to simulate isotope tracers in air pollution. The model contains 16 N compounds, and 96 reactions involving N used in the Regional Atmospheric Chemistry Mechanism (RACM) were replicated using 15N in a new mechanism called iNRACM. The model is able to predict d15N variations in NOx, HONO, and HNO3 that are similar to those observed in aerosol and gases in the troposphere.
Veronica R. Rollinson, Julie Granger, Sydney C. Clark, Mackenzie L. Blanusa, Claudia P. Koerting, Jamie M. P. Vaudrey, Lija A. Treibergs, Holly C. Westbrook, Catherine M. Matassa, Meredith G. Hastings, and Craig R. Tobias
Biogeosciences, 18, 3421–3444, https://doi.org/10.5194/bg-18-3421-2021, https://doi.org/10.5194/bg-18-3421-2021, 2021
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We measured nutrients and the naturally occurring nitrogen (N) and oxygen (O) stable isotope ratios of nitrate discharged from a New England river over an annual cycle, to monitor N loading and identify dominant sources from the watershed. We uncovered a seasonality to loading and sources of N from the watershed. Seasonality in the nitrate isotope ratios also informed on N cycling, conforming to theoretical expectations of riverine nutrient cycling.
Paul T. Griffiths, Lee T. Murray, Guang Zeng, Youngsub Matthew Shin, N. Luke Abraham, Alexander T. Archibald, Makoto Deushi, Louisa K. Emmons, Ian E. Galbally, Birgit Hassler, Larry W. Horowitz, James Keeble, Jane Liu, Omid Moeini, Vaishali Naik, Fiona M. O'Connor, Naga Oshima, David Tarasick, Simone Tilmes, Steven T. Turnock, Oliver Wild, Paul J. Young, and Prodromos Zanis
Atmos. Chem. Phys., 21, 4187–4218, https://doi.org/10.5194/acp-21-4187-2021, https://doi.org/10.5194/acp-21-4187-2021, 2021
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We analyse the CMIP6 Historical and future simulations for tropospheric ozone, a species which is important for many aspects of atmospheric chemistry. We show that the current generation of models agrees well with observations, being particularly successful in capturing trends in surface ozone and its vertical distribution in the troposphere. We analyse the factors that control ozone and show that they evolve over the period of the CMIP6 experiments.
Vasilii V. Petrenko, Andrew M. Smith, Edward M. Crosier, Roxana Kazemi, Philip Place, Aidan Colton, Bin Yang, Quan Hua, and Lee T. Murray
Atmos. Meas. Tech., 14, 2055–2063, https://doi.org/10.5194/amt-14-2055-2021, https://doi.org/10.5194/amt-14-2055-2021, 2021
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This paper presents an improved methodology for measurements of atmospheric concentration of carbon-14-containing carbon monoxide (14CO), as well as a 1-year dataset that demonstrates the methodology. Atmospheric 14CO concentration measurements are useful for improving the understanding of spatial and temporal variability of hydroxyl radical concentrations. Key improvements over prior methods include a greatly reduced air sample size and accurate procedural blank characterization.
Guitao Shi, Hongmei Ma, Zhengyi Hu, Zhenlou Chen, Chunlei An, Su Jiang, Yuansheng Li, Tianming Ma, Jinhai Yu, Danhe Wang, Siyu Lu, Bo Sun, and Meredith G. Hastings
The Cryosphere, 15, 1087–1095, https://doi.org/10.5194/tc-15-1087-2021, https://doi.org/10.5194/tc-15-1087-2021, 2021
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It is important to understand atmospheric chemistry over Antarctica under a changing climate. Thus snow collected on a traverse from the coast to Dome A was used to investigate variations in snow chemistry. The non-sea-salt fractions of K+, Mg2+, and Ca2+ are associated with terrestrial inputs, and nssCl− is from HCl. In general, proportions of non-sea-salt fractions of ions to the totals are higher in the interior areas than on the coast, and the proportions are higher in summer than in winter.
David S. Stevenson, Alcide Zhao, Vaishali Naik, Fiona M. O'Connor, Simone Tilmes, Guang Zeng, Lee T. Murray, William J. Collins, Paul T. Griffiths, Sungbo Shim, Larry W. Horowitz, Lori T. Sentman, and Louisa Emmons
Atmos. Chem. Phys., 20, 12905–12920, https://doi.org/10.5194/acp-20-12905-2020, https://doi.org/10.5194/acp-20-12905-2020, 2020
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We present historical trends in atmospheric oxidizing capacity (OC) since 1850 from the latest generation of global climate models and compare these with estimates from measurements. OC controls levels of many key reactive gases, including methane (CH4). We find small model trends up to 1980, then increases of about 9 % up to 2014, disagreeing with (uncertain) measurement-based trends. Major drivers of OC trends are emissions of CH4, NOx, and CO; these will be important for future CH4 trends.
Wendell W. Walters, Linlin Song, Jiajue Chai, Yunting Fang, Nadia Colombi, and Meredith G. Hastings
Atmos. Chem. Phys., 20, 11551–11567, https://doi.org/10.5194/acp-20-11551-2020, https://doi.org/10.5194/acp-20-11551-2020, 2020
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This article details new field observations of the nitrogen stable isotopic composition of ammonia emitted from vehicles conducted in the US and China. Vehicle emissions of ammonia may be a significant source to urban regions with important human health and environmental implications. Our measurements have indicated a consistent isotopic signature from vehicle ammonia emissions. The nitrogen isotopic composition of ammonia may be a useful tool for tracking vehicle emissions.
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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.
Atmospheric nitrate has an important impact on human and ecosystem health. We evaluated...
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