Articles | Volume 24, issue 8
https://doi.org/10.5194/acp-24-4895-2024
© Author(s) 2024. 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-24-4895-2024
© Author(s) 2024. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
25 Apr 2024
Research article |
| 25 Apr 2024
| 25 Apr 2024
An inverse model to correct for the effects of post-depositional processing on ice-core nitrate and its isotopes: model framework and applications at Summit, Greenland, and Dome C, Antarctica
Zhuang Jiang
School of Earth and Space Sciences, University of Science and Technology of China, Hefei, Anhui, China
Becky Alexander
Department of Atmospheric Sciences, University of Washington, Seattle WA, USA
Joel Savarino
IGE, Univ. Grenoble Alpes, CNRS, IRD, Grenoble INP, INRAE, Grenoble, France
School of Earth and Space Sciences, University of Science and Technology of China, Hefei, Anhui, China
Deep Space Exploration Laboratory, Hefei, Anhui, China
CAS Center for Excellence in Comparative Planetology, University of Science and Technology of China, Hefei, Anhui, China
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Accurate prediction of aerosol pH in chemical transport models is essential to aerosol modeling. This study examines the performance of the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem) on aerosol pH predictions and the sensitivities to emissions of nonvolatile cations and NH3, aerosol-phase state assumption, and heterogeneous sulfate production. Temporal evolution of aerosol pH during haze cycles in Beijing and the driving factors are also presented and discussed.
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The ~ 74 ka eruption of Toba was one of the largest eruptions of the last 100 ka. We have measured the sulfur isotopic composition for 11 Toba eruption candidates in two Antarctic ice cores. Sulfur isotopes allow us to distinguish between large eruptions that have erupted material into the stratosphere and smaller ones that reach lower altitudes. Using this we have identified the events most likely to be Toba and place the eruption on the transition into a cold period in the Northern Hemisphere.
Xuan Wang, Daniel J. Jacob, William Downs, Shuting Zhai, Lei Zhu, Viral Shah, Christopher D. Holmes, Tomás Sherwen, Becky Alexander, Mathew J. Evans, Sebastian D. Eastham, J. Andrew Neuman, Patrick R. Veres, Theodore K. Koenig, Rainer Volkamer, L. Gregory Huey, Thomas J. Bannan, Carl J. Percival, Ben H. Lee, and Joel A. Thornton
Atmos. Chem. Phys., 21, 13973–13996, https://doi.org/10.5194/acp-21-13973-2021, https://doi.org/10.5194/acp-21-13973-2021, 2021
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Halogen radicals have a broad range of implications for tropospheric chemistry, air quality, and climate. We present a new mechanistic description and comprehensive simulation of tropospheric halogens in a global 3-D model and compare the model results with surface and aircraft measurements. We find that halogen chemistry decreases the global tropospheric burden of ozone by 11 %, NOx by 6 %, and OH by 4 %.
Andreas Tilgner, Thomas Schaefer, Becky Alexander, Mary Barth, Jeffrey L. Collett Jr., Kathleen M. Fahey, Athanasios Nenes, Havala O. T. Pye, Hartmut Herrmann, and V. Faye McNeill
Atmos. Chem. Phys., 21, 13483–13536, https://doi.org/10.5194/acp-21-13483-2021, https://doi.org/10.5194/acp-21-13483-2021, 2021
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Feedbacks of acidity and atmospheric multiphase chemistry in deliquesced particles and clouds are crucial for the tropospheric composition, depositions, climate, and human health. This review synthesizes the current scientific knowledge on these feedbacks using both inorganic and organic aqueous-phase chemistry. Finally, this review outlines atmospheric implications and highlights the need for future investigations with respect to reducing emissions of key acid precursors in a changing world.
Zhuang Jiang, Becky Alexander, Joel Savarino, Joseph Erbland, and Lei Geng
The Cryosphere, 15, 4207–4220, https://doi.org/10.5194/tc-15-4207-2021, https://doi.org/10.5194/tc-15-4207-2021, 2021
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We used a snow photochemistry model (TRANSITS) to simulate the seasonal nitrate snow profile at Summit, Greenland. Comparisons between model outputs and observations suggest that at Summit post-depositional processing is active and probably dominates the snowpack δ15N seasonality. We also used the model to assess the degree of snow nitrate loss and the consequences in its isotopes at present and in the past, which helps for quantitative interpretations of ice-core nitrate records.
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.
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.
Cited articles
Abbatt, J. P. D.: Interaction of HNO3 with water-ice surfaces at temperatures of the free troposphere, Geophys. Res. Lett., 24, 1479–1482, https://doi.org/10.1029/97GL01403, 1997.
Akers, P. D., Savarino, J., Caillon, N., Magand, O., and Le Meur, E.: Photolytic modification of seasonal nitrate isotope cycles in East Antarctica, Atmos. Chem. Phys., 22, 15637–15657, https://doi.org/10.5194/acp-22-15637-2022, 2022a.
Akers, P. D., Savarino, J., Caillon, N., Servettaz, A. P. M., Le Meur, E., Magand, O., Martins, J., Agosta, C., Crockford, P., Kobayashi, K., Hattori, S., Curran, M., van Ommen, T., Jong, L., and Roberts, J. L.: Sunlight-driven nitrate loss records Antarctic surface mass balance, Nat. Commun., 13, 4274, https://doi.org/10.1038/s41467-022-31855-7, 2022b.
Alexander, B. and Mickley, L. J.: Paleo-perspectives on potential future changes in the oxidative capacity of the atmosphere due to climate change and anthropogenic emissions, Curr. Pollut. Rep., 1, 57–69, https://doi.org/10.1007/s40726-015-0006-0, 2015.
Alexander, B., Savarino, J., Kreutz, K. J., and Thiemens, M. H.: Impact of preindustrial biomass-burning emissions on the oxidation pathways of tropospheric sulfur and nitrogen, J. Geophys. Res., 109, D08303, https://doi.org/10.1029/2003JD004218, 2004.
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.
Bennartz, R., Fell, F., Pettersen, C., Shupe, M. D., and Schuettemeyer, D.: Spatial and temporal variability of snowfall over Greenland from CloudSat observations, Atmos. Chem. Phys., 19, 8101–8121, https://doi.org/10.5194/acp-19-8101-2019, 2019.
Berhanu, T. A., Meusinger, C., Erbland, J., Jost, R., Bhattacharya, S. K., Johnson, M. S., and Savarino, J.: Laboratory study of nitrate photolysis in Antarctic snow. II. Isotopic effects and wavelength dependence, J. Chem. Phys., 140, 244306, https://doi.org/10.1063/1.4882899, 2014.
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.
Burkhart, J. F., Hutterli, M., Bales, R. C., and McConnell, J. R.: Seasonal accumulation timing and preservation of nitrate in firn at Summit, Greenland, J. Geophys. Res.-Atmos., 109, D22309, https://doi.org/10.1029/2004JD004658, 2004.
Castellani, B. B., Shupe, M. D., Hudak, D. R., and Sheppard, B. E.: The annual cycle of snowfall at Summit, Greenland, J. Geophys. Res.-Atmos., 120, 6654–6668, https://doi.org/10.1002/2015JD023072, 2015.
Chu, L. and Anastasio, C.: Quantum Yields of Hydroxyl Radical and Nitrogen Dioxide from the Photolysis of Nitrate on Ice, J. Phys. Chem. A, 107, 9594–9602, https://doi.org/10.1021/jp0349132, 2003.
Dibb, J. E. and Fahnestock, M.: Snow accumulation, surface height change, and firn densification at Summit, Greenland: Insights from 2 years of in situ observation, J. Geophys. Res.-Atmos., 109, D24113, https://doi.org/10.1029/2003JD004300, 2004.
Dibb, J. E., Talbot, R. W., Whitlow, S. I., Shipham, M. C., Winterle, J., McConnell, J., and Bales, R.: Biomass burning signatures in the atmosphere and snow at Summit, Greenland: An event on 5 August 1994, Atmos. Environ., 30, 553–561, https://doi.org/10.1016/1352-2310(95)00328-2, 1996.
Dibb, J. E., Talbot, R. W., Munger, J. W., Jacob, D. J., and Fan, S. M.: Air-snow exchange of HNO3 and NOy at Summit, Greenland, J. Geophys. Res.-Atmos., 103, 3475–3486, https://doi.org/10.1029/97JD03132, 1998.
Dibb, J. E., Whitlow, S. I., and Arsenault, M.: Seasonal variations in the soluble ion content of snow at Summit. Greenland: Constraints from three years of daily surface snow samples, Atmos. Environ., 41, 5007–5019, https://doi.org/10.1016/j.atmosenv.2006.12.010, 2007.
Erbland, J., Vicars, W. C., Savarino, J., Morin, S., Frey, M. M., Frosini, D., Vince, E., and Martins, J. M. F.: Air–snow transfer of nitrate on the East Antarctic Plateau – Part 1: Isotopic evidence for a photolytically driven dynamic equilibrium in summer, Atmos. Chem. Phys., 13, 6403–6419, https://doi.org/10.5194/acp-13-6403-2013, 2013.
Erbland, J., Savarino, J., Morin, S., France, J. L., Frey, M. M., and King, M. D.: Air–snow transfer of nitrate on the East Antarctic Plateau – Part 2: An isotopic model for the interpretation of deep ice-core records, Atmos. Chem. Phys., 15, 12079–12113, https://doi.org/10.5194/acp-15-12079-2015, 2015.
Esquivel-Hernández, G., Matiatos, I., Sánchez-Murillo, R., Vystavna, Y., Balestrini, R., Wells, N. S., Monteiro, L. R., Chantara, S., Walters, W., and Wassenaar, L. I.: Nitrate isotopes (δ15N, δ18O) in precipitation: best practices from an international coordinated research project, Isot. Environ. Healt. S., 59, 127–141, https://doi.org/10.1080/10256016.2023.2177649, 2023.
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.
Fibiger, D. L., Dibb, J. E., Chen, D., Thomas, J. L., Burkhart, J. F., Huey, L. G., and Hastings, M. G.: Analysis of nitrate in the snow and atmosphere at Summit, Greenland: Chemistry and transport, J. Geophys. Res.-Atmos., 121, 5010–5030, https://doi.org/10.1002/2015JD024187, 2016.
Fischer, H., Wagenbach, D., and Kipfstuhl, J.: Sulfate and nitrate firn concentrations on the Greenland ice sheet: 2. Temporal anthropogenic deposition changes, J. Geophys. Res.-Atmos., 103, 21935–21942, https://doi.org/10.1029/98JD01886, 1998.
Frey, M. M., Savarino, J., Morin, S., Erbland, J., and Martins, J. M. F.: Photolysis imprint in the nitrate stable isotope signal in snow and atmosphere of East Antarctica and implications for reactive nitrogen cycling, Atmos. Chem. Phys., 9, 8681–8696, https://doi.org/10.5194/acp-9-8681-2009, 2009.
Freyer, H. D.: Seasonal variation of
Furukawa, R., Uemura, R., Fujita, K., Sjolte, J., Yoshimura, K., Matoba, S., and Iizuka, Y.: Seasonal-Scale Dating of a Shallow Ice Core From Greenland Using Oxygen Isotope Matching Between Data and Simulation, J. Geophys. Res.-Atmos., 122, 10873–10887, https://doi.org/10.1002/2017JD026716, 2017.
Gao, Y., Zhou, F., Ciais, P., Miao, C., Yang, T., Jia, Y., Zhou, X., Klaus, B.-B., Yang, T., and Yu, G.: Human activities aggravate nitrogen-deposition pollution to inland water over China, Natl. Sci. Rev., 7, 430–440, https://doi.org/10.1093/nsr/nwz073, 2019.
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.
Geng, L., Zatko, M. C., Alexander, B., Fudge, T. J., Schauer, A. J., Murray, L. T., and Mickley, L. J.: Effects of post-depositional processing on nitrogen isotopes of nitrate in the Greenland Ice Sheet Project 2 ice core, 42, 5346–5354, https://doi.org/10.1002/2015GL064218, 2015.
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.
Hastings, M. G., Steig, E. J., and Sigman, D. M.: Seasonal variations in N and O isotopes of nitrate in snow at Summit, Greenland: Implications for the study of nitrate in snow and ice cores, J. Geophys. Res., 109, D20306, https://doi.org/10.1029/2004JD004991, 2004.
Hastings, M. G., Sigman, D. M., and Steig, E. J.: Glacial/interglacial changes in the isotopes of nitrate from the Greenland Ice Sheet Project 2 (GISP2) ice core, Global Biogeochem. Cy., 19, GB4024, https://doi.org/10.1029/2005GB002502, 2005.
Heaton, T. H. E.: 15N14N ratios of nitrate and ammonium in rain at Pretoria, South Africa, Atmos. Environ., 21, 843–852, https://doi.org/10.1016/0004-6981(87)90080-1, 1987.
Honrath, R., Lu, Y., Peterson, M. C., Dibb, J. E., Arsenault, M., Cullen, N., and Steffen, K. J. A. E.: Vertical fluxes of NOx, HONO, and HNO3 above the snowpack at Summit, Greenland, Atmos. Environ., 36, 2629–2640, 2002.
Iizuka, Y., Uemura, R., Fujita, K., Hattori, S., Seki, O., Miyamoto, C., Suzuki, T., Yoshida, N., Motoyama, H., and Matoba, S.: A 60 Year Record of Atmospheric Aerosol Depositions Preserved in a High-Accumulation Dome Ice Core, Southeast Greenland, J. Geophys. Res.-Atmos., 123, 574–589, https://doi.org/10.1002/2017JD026733, 2018.
Ishino, S., Hattori, S., Savarino, J., Jourdain, B., Preunkert, S., Legrand, M., Caillon, N., Barbero, A., Kuribayashi, K., and Yoshida, N.: Seasonal variations of triple oxygen isotopic compositions of atmospheric sulfate, nitrate, and ozone at Dumont d'Urville, coastal Antarctica, Atmos. Chem. Phys., 17, 3713–3727, https://doi.org/10.5194/acp-17-3713-2017, 2017.
Jiang, Z.: The inverse model code, Zenodo [code, data set], https://doi.org/10.5281/zenodo.10805443, 2024.
Jiang, Z., Alexander, B., Savarino, J., Erbland, J., and Geng, L.: Impacts of the photo-driven post-depositional processing on snow nitrate and its isotopes at Summit, Greenland: a model-based study, The Cryosphere, 15, 4207–4220, https://doi.org/10.5194/tc-15-4207-2021, 2021.
Jiang, Z., Savarino, J., Alexander, B., Erbland, J., Jaffrezo, J.-L., and Geng, L.: Impacts of post-depositional processing on nitrate isotopes in the snow and the overlying atmosphere at Summit, Greenland, The Cryosphere, 16, 2709–2724, https://doi.org/10.5194/tc-16-2709-2022, 2022.
Kahl, J. D. W., Martinez, D. A., Kuhns, H., Davidson, C. I., Jaffrezo, J.-L., and Harris, J. M.: Air mass trajectories to Summit, Greenland: A 44-year climatology and some episodic events, J. Geophys. Res.-Oceans, 102, 26861–26875, https://doi.org/10.1029/97JC00296, 1997.
Krankowsky, D., Lämmerzahl, P., and Mauersberger, K.: Isotopic measurements of stratospheric ozone, Geophys. Res. Lett., 27, 2593–2595, https://doi.org/10.1029/2000GL011812, 2000.
Lämmerzahl, P., Röckmann, T., Brenninkmeijer, C. A. M., Krankowsky, D., and Mauersberger, K.: Oxygen isotope composition of stratospheric carbon dioxide, Geophys. Res. Lett., 29, 23-21–23-24, https://doi.org/10.1029/2001GL014343, 2002.
Lee, H.-M., Henze, D. K., Alexander, B., and Murray, L. T.: Investigating the sensitivity of surface-level nitrate seasonality in Antarctica to primary sources using a global model, Atmos. Environ., 89, 757–767, https://doi.org/10.1016/j.atmosenv.2014.03.003, 2014.
Legrand, M. R. and Delmas, R. J.: Relative contributions of tropospheric and stratospheric sources to nitrate in Antarctic snow, Tellus B, 38, 236–249, https://doi.org/10.3402/tellusb.v38i3-4.15132, 1986.
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, Y., Shi, G., Chen, Z., Lan, M., Ding, M., Li, Z., and Hastings, M. G.: Significant Latitudinal Gradient of Nitrate Production in the Marine Atmospheric Boundary Layer of the Northern Hemisphere, Geophys. Res., Lett., 49, e2022GL100503, https://doi.org/10.1029/2022GL100503, 2022.
Lim, S., Lee, M., Savarino, J., and Laj, P.: Oxidation pathways and emission sources of atmospheric particulate nitrate in Seoul: based on δ15N and Δ17O measurements, Atmos. Chem. Phys., 22, 5099–5115, https://doi.org/10.5194/acp-22-5099-2022, 2022.
Lyons, J. R.: Transfer of mass-independent fractionation in ozone to other oxygen-containing radicals in the atmosphere, Geophys. Res. Lett., 28, 3231–3234, https://doi.org/10.1029/2000GL012791, 2001.
Madronich, S., McKenzie, R. L., Björn, L. O., and Caldwell, M. M.: Changes in biologically active ultraviolet radiation reaching the Earth's surface, J. Photoch. Photobio. B, 46, 5–19, https://doi.org/10.1016/S1011-1344(98)00182-1, 1998.
Mauersberger, K., Krankowsky, D., and Janssen, C.: Oxygen Isotope Processes and Transfer Reactions, Space Sci. Rev., 106, 265–279, https://doi.org/10.1023/A:1024650007258, 2003.
McCabe, J. R., Boxe, C. S., Colussi, A. J., Hoffmann, M. R., and Thiemens, M. H.: Oxygen isotopic fractionation in the photochemistry of nitrate in water and ice, J. Geophys. Res., 110, D15310, https://doi.org/10.1029/2004JD005484, 2005.
Meusinger, C., Berhanu, T. A., Erbland, J., Savarino, J., and Johnson, M. S.: Laboratory study of nitrate photolysis in Antarctic snow. I. Observed quantum yield, domain of photolysis, and secondary chemistry, J. Chem. Phys., 140, 244305, https://doi.org/10.1063/1.4882898, 2014.
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., Savarino, J., Frey, M. M., Domine, F., Jacobi, H.-W., Kaleschke, L., and Martins, J. M. F.: Comprehensive isotopic composition of atmospheric nitrate in the Atlantic Ocean boundary layer from 65° S to 79° N, J. Geophys. Res., 114, D05303, https://doi.org/10.1029/2008JD010696, 2009.
Morin, S., Erbland, J., Savarino, J., Domine, F., Bock, J., Friess, U., Jacobi, H.-W., Sihler, H., and Martins, J. M. F.: An isotopic view on the connection between photolytic emissions of NOx from the Arctic snowpack and its oxidation by reactive halogens, J. Geophys. Res., 117, D00R08, https://doi.org/10.1029/2011JD016618, 2012.
Murray, L. T., Mickley, L. J., Kaplan, J. O., Sofen, E. D., Pfeiffer, M., and Alexander, B.: Factors controlling variability in the oxidative capacity of the troposphere since the Last Glacial Maximum, Atmos. Chem. Phys., 14, 3589–3622, https://doi.org/10.5194/acp-14-3589-2014, 2014.
Murray, L. T., Leibensperger, E. M., Orbe, C., Mickley, L. J., and Sulprizio, M.: GCAP 2.0: a global 3-D chemical-transport model framework for past, present, and future climate scenarios, Geosci. Model Dev., 14, 5789–5823, https://doi.org/10.5194/gmd-14-5789-2021, 2021.
Pilegaard, K., Skiba, U., Ambus, P., Beier, C., Brüggemann, N., Butterbach-Bahl, K., Dick, J., Dorsey, J., Duyzer, J., Gallagher, M., Gasche, R., Horvath, L., Kitzler, B., Leip, A., Pihlatie, M. K., Rosenkranz, P., Seufert, G., Vesala, T., Westrate, H., and Zechmeister-Boltenstern, S.: Factors controlling regional differences in forest soil emission of nitrogen oxides (NO and N2O), Biogeosciences, 3, 651–661, https://doi.org/10.5194/bg-3-651-2006, 2006.
Quinn, P. K., Shaw, G., Andrews, E., Dutton, E. G., Ruoho-Airola, T., and Gong, S. L.: Arctic haze: current trends and knowledge gaps, Tellus B, 59, 99–114, https://doi.org/10.1111/j.1600-0889.2006.00238.x, 2007.
Röthlisberger, R., Hutterli, M. A., Sommer, S., Wolff, E. W., and Mulvaney, R.: Factors controlling nitrate in ice cores: Evidence from the Dome C deep ice core, J. Geophys. Res.-Atmos., 105, 20565–20572, https://doi.org/10.1029/2000JD900264, 2000.
Savarino, J., Kaiser, J., Morin, S., Sigman, D. M., and Thiemens, M. H.: Nitrogen and oxygen isotopic constraints on the origin of atmospheric nitrate in coastal Antarctica, Atmos. Chem. Phys., 7, 1925–1945, https://doi.org/10.5194/acp-7-1925-2007, 2007.
Savarino, J., Bhattacharya, S. K., Morin, S., Baroni, M., and Doussin, J.-F.: The NO + O3 reaction: A triple oxygen isotope perspective on the reaction dynamics and atmospheric implications for the transfer of the ozone isotope anomaly, J. Chem. Phys., 128, 194303, https://doi.org/10.1063/1.2917581, 2008.
Savarino, J., Vicars, W. C., Legrand, M., Preunkert, S., Jourdain, B., Frey, M. M., Kukui, A., Caillon, N., and Gil Roca, J.: Oxygen isotope mass balance of atmospheric nitrate at Dome C, East Antarctica, during the OPALE campaign, Atmos. Chem. Phys., 16, 2659–2673, https://doi.org/10.5194/acp-16-2659-2016, 2016.
Seinfeld, J. H. and Pandis, S. N.: Atmospheric chemistry and physics: from air pollution to climate change, John Wiley & Sons, ISBN 978-1-118-94740-1, 2016.
Shi, G., Buffen, A. M., Hastings, M. G., Li, C., Ma, H., Li, Y., Sun, B., An, C., and Jiang, S.: Investigation of post-depositional processing of nitrate in East Antarctic snow: isotopic constraints on photolytic loss, re-oxidation, and source inputs, Atmos. Chem. Phys., 15, 9435–9453, https://doi.org/10.5194/acp-15-9435-2015, 2015.
Shi, G., Buffen, A. M., Ma, H., Hu, Z., Sun, B., Li, C., Yu, J., Ma, T., An, C., Jiang, S., Li, Y., and Hastings, M. G.: Distinguishing summertime atmospheric production of nitrate across the East Antarctic Ice Sheet, Geochim. Cosmochim. Ac., 231, 1–14, https://doi.org/10.1016/j.gca.2018.03.025, 2018.
Shi, G., Ma, H., Zhu, Z., Hu, Z., Chen, Z., Jiang, S., An, C., Yu, J., Ma, T., Li, Y., Sun, B., and Hastings, M. G.: Using stable isotopes to distinguish atmospheric nitrate production and its contribution to the surface ocean across hemispheres, Earth Planet. Sc. Lett., 564, 116914, https://doi.org/10.1016/j.epsl.2021.116914, 2021.
Shi, G., Li, C., Li, Y., Chen, Z., Ding, M., Ma, H., Jiang, S., An, C., Guo, J., Sun, B., and Hastings, M. G.: Isotopic constraints on sources, production, and phase partitioning for nitrate in the atmosphere and snowfall in coastal East Antarctica, Earth Planet. Sc. Lett., 578, 117300, https://doi.org/10.1016/j.epsl.2021.117300, 2022.
Shi, G., Buffen, A. M., Hu, Y., Chai, J., Li, Y., Wang, D., and Hastings, M. G.: Modeling the Complete Nitrogen and Oxygen Isotopic Imprint of Nitrate Photolysis in Snow, Geophys. Res. Lett., 50, e2023GL103778, https://doi.org/10.1029/2023GL103778, 2023.
Sillman, S.: The relation between ozone, NOx and hydrocarbons in urban and polluted rural environments, Atmos. Environ., 33, 1821–1845, https://doi.org/10.1016/S1352-2310(98)00345-8, 1999.
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.
Vicars, W. C. and Savarino, J.: Quantitative constraints on the 17O-excess (Δ17O) signature of surface ozone: Ambient measurements from 50° N to 50° S using the nitrite-coated filter technique, Geochim. Cosmochim. Ac., 135, 270–287, https://doi.org/10.1016/j.gca.2014.03.023, 2014.
Walters, W. W., Michalski, G., Böhlke, J. K., Alexander, B., Savarino, J., and Thiemens, M. H.: Assessing the Seasonal Dynamics of Nitrate and Sulfate Aerosols at the South Pole Utilizing Stable Isotopes, J. Geophys. Res.-Atmos., 124, 8161–8177, https://doi.org/10.1029/2019JD030517, 2019.
Winton, V. H. L., Ming, A., Caillon, N., Hauge, L., Jones, A. E., Savarino, J., Yang, X., and Frey, M. M.: Deposition, recycling, and archival of nitrate stable isotopes between the air–snow interface: comparison between Dronning Maud Land and Dome C, Antarctica , Atmos. Chem. Phys., 20, 5861–5885, https://doi.org/10.5194/acp-20-5861-2020, 2020.
Wolff, E. W.: Nitrate in polar ice, Ice core studies of global biogeochemical cycles, Springer, Berlin, Heidelberg, 195–224, https://doi.org/10.1007/978-3-642-51172-1_10, 1995.
Wolff, E. W., Jones, A. E., Bauguitte, S. J.-B., and Salmon, R. A.: The interpretation of spikes and trends in concentration of nitrate in polar ice cores, based on evidence from snow and atmospheric measurements, Atmos. Chem. Phys., 8, 5627–5634, https://doi.org/10.5194/acp-8-5627-2008, 2008.
Zatko, M., Erbland, J., Savarino, J., Geng, L., Easley, L., Schauer, A., Bates, T., Quinn, P. K., Light, B., Morison, D., Osthoff, H. D., Lyman, S., Neff, W., Yuan, B., and Alexander, B.: The magnitude of the snow-sourced reactive nitrogen flux to the boundary layer in the Uintah Basin, Utah, USA, Atmos. Chem. Phys., 16, 13837–13851, https://doi.org/10.5194/acp-16-13837-2016, 2016.
Zatko, M. C., Grenfell, T. C., Alexander, B., Doherty, S. J., Thomas, J. L., and Yang, X.: The influence of snow grain size and impurities on the vertical profiles of actinic flux and associated NOx emissions on the Antarctic and Greenland ice sheets, Atmos. Chem. Phys., 13, 3547–3567, https://doi.org/10.5194/acp-13-3547-2013, 2013.
Zhang, L., Jacob, D. J., Knipping, E. M., Kumar, N., Munger, J. W., Carouge, C. C., van Donkelaar, A., Wang, Y. X., and Chen, D.: Nitrogen deposition to the United States: distribution, sources, and processes, Atmos. Chem. Phys., 12, 4539–4554, https://doi.org/10.5194/acp-12-4539-2012, 2012.
Short summary
Ice-core nitrate could track the past atmospheric NOx and oxidant level, but its interpretation is hampered by the post-depositional processing. In this work, an inverse model was developed and tested against two polar sites and was shown to well reproduce the observed nitrate signals in snow and atmosphere, suggesting that the model can properly correct for the effect of post-depositional processing. This model offers a very useful tool for future studies on ice-core nitrate records.
Ice-core nitrate could track the past atmospheric NOx and oxidant level, but its interpretation...
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