Articles | Volume 20, issue 16
https://doi.org/10.5194/acp-20-9805-2020
© Author(s) 2020. 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-20-9805-2020
© Author(s) 2020. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Research article
| 
21 Aug 2020
Research article |
| 21 Aug 2020
| 21 Aug 2020
Quantifying the nitrogen isotope effects during photochemical equilibrium between NO and NO2: implications for δ15N in tropospheric reactive nitrogen
Department of Earth, Atmospheric and Planetary Sciences, Purdue
University, West Lafayette, IN, 47907, USA
Xuan Zhang
Atmospheric Chemistry Observations and Modeling Lab, National
Center for Atmospheric Research, Boulder, CO, 80301, USA
John Orlando
Atmospheric Chemistry Observations and Modeling Lab, National
Center for Atmospheric Research, Boulder, CO, 80301, USA
Geoffrey Tyndall
Atmospheric Chemistry Observations and Modeling Lab, National
Center for Atmospheric Research, Boulder, CO, 80301, USA
Greg Michalski
Department of Earth, Atmospheric and Planetary Sciences, Purdue
University, West Lafayette, IN, 47907, USA
Department of Chemistry, Purdue University, West Lafayette, IN,
47907, USA
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Chelsea R. Thompson, Paul B. Shepson, Jin Liao, L. Greg Huey, Chris Cantrell, Frank Flocke, and John Orlando
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Xuan Zhang, Jordan E. Krechmer, Michael Groessl, Wen Xu, Stephan Graf, Michael Cubison, John T. Jayne, Jose L. Jimenez, Douglas R. Worsnop, and Manjula R. Canagaratna
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Justin H. Dingle, Kennedy Vu, Roya Bahreini, Eric C. Apel, Teresa L. Campos, Frank Flocke, Alan Fried, Scott Herndon, Alan J. Hills, Rebecca S. Hornbrook, Greg Huey, Lisa Kaser, Denise D. Montzka, John B. Nowak, Mike Reeves, Dirk Richter, Joseph R. Roscioli, Stephen Shertz, Meghan Stell, David Tanner, Geoff Tyndall, James Walega, Petter Weibring, and Andrew Weinheimer
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Theodora Nah, Renee C. McVay, Xuan Zhang, Christopher M. Boyd, John H. Seinfeld, and Nga L. Ng
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Atmos. Meas. Tech., 9, 3245–3262, https://doi.org/10.5194/amt-9-3245-2016, https://doi.org/10.5194/amt-9-3245-2016, 2016
Renee C. McVay, Xuan Zhang, Bernard Aumont, Richard Valorso, Marie Camredon, Yuyi S. La, Paul O. Wennberg, and John H. Seinfeld
Atmos. Chem. Phys., 16, 2785–2802, https://doi.org/10.5194/acp-16-2785-2016, https://doi.org/10.5194/acp-16-2785-2016, 2016
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V. Shah, L. Jaeglé, L. E. Gratz, J. L. Ambrose, D. A. Jaffe, N. E. Selin, S. Song, T. L. Campos, F. M. Flocke, M. Reeves, D. Stechman, M. Stell, J. Festa, J. Stutz, A. J. Weinheimer, D. J. Knapp, D. D. Montzka, G. S. Tyndall, E. C. Apel, R. S. Hornbrook, A. J. Hills, D. D. Riemer, N. J. Blake, C. A. Cantrell, and R. L. Mauldin III
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K. D. Custard, C. R. Thompson, K. A. Pratt, P B. Shepson, J. Liao, L. G. Huey, J. J. Orlando, A. J. Weinheimer, E. Apel, S. R. Hall, F. Flocke, L. Mauldin, R. S. Hornbrook, D. Pöhler, S. General, J. Zielcke, W. R. Simpson, U. Platt, A. Fried, P. Weibring, B. C. Sive, K. Ullmann, C. Cantrell, D. J. Knapp, and D. D. Montzka
Atmos. Chem. Phys., 15, 10799–10809, https://doi.org/10.5194/acp-15-10799-2015, https://doi.org/10.5194/acp-15-10799-2015, 2015
C. R. Thompson, P. B. Shepson, J. Liao, L. G. Huey, E. C. Apel, C. A. Cantrell, F. Flocke, J. Orlando, A. Fried, S. R. Hall, R. S. Hornbrook, D. J. Knapp, R. L. Mauldin III, D. D. Montzka, B. C. Sive, K. Ullmann, P. Weibring, and A. Weinheimer
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A. Hodzic, S. Madronich, P. S. Kasibhatla, G. Tyndall, B. Aumont, J. L. Jimenez, J. Lee-Taylor, and J. Orlando
Atmos. Chem. Phys., 15, 9253–9269, https://doi.org/10.5194/acp-15-9253-2015, https://doi.org/10.5194/acp-15-9253-2015, 2015
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R. Thalman, M. T. Baeza-Romero, S. M. Ball, E. Borrás, M. J. S. Daniels, I. C. A. Goodall, S. B. Henry, T. Karl, F. N. Keutsch, S. Kim, J. Mak, P. S. Monks, A. Muñoz, J. Orlando, S. Peppe, A. R. Rickard, M. Ródenas, P. Sánchez, R. Seco, L. Su, G. Tyndall, M. Vázquez, T. Vera, E. Waxman, and R. Volkamer
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Measurements of α-dicarbonyl compounds, like glyoxal (CHOCHO) and methyl glyoxal (CH3C(O)CHO), are informative about the rate of hydrocarbon oxidation, oxidative capacity, and secondary organic aerosol (SOA) formation in the atmosphere. We have compared nine instruments and seven techniques to measure α-dicarbonyl, using simulation chamber facilities in the US and Europe. We assess our understanding of calibration, precision, accuracy and detection limits, as well as possible sampling biases.
X. Zhang, R. H. Schwantes, R. C. McVay, H. Lignell, M. M. Coggon, R. C. Flagan, and J. H. Seinfeld
Atmos. Chem. Phys., 15, 4197–4214, https://doi.org/10.5194/acp-15-4197-2015, https://doi.org/10.5194/acp-15-4197-2015, 2015
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We present an experimental protocol to constrain the nature of organic vapor--wall deposition in Teflon chambers and develop an empirical model to predict the wall-induced deposition rate of intermediate/semi/non-volatility organic vapors in chambers.
T. B. Nguyen, J. D. Crounse, R. H. Schwantes, A. P. Teng, K. H. Bates, X. Zhang, J. M. St. Clair, W. H. Brune, G. S. Tyndall, F. N. Keutsch, J. H. Seinfeld, and P. O. Wennberg
Atmos. Chem. Phys., 14, 13531–13549, https://doi.org/10.5194/acp-14-13531-2014, https://doi.org/10.5194/acp-14-13531-2014, 2014
C. Knote, A. Hodzic, J. L. Jimenez, R. Volkamer, J. J. Orlando, S. Baidar, J. Brioude, J. Fast, D. R. Gentner, A. H. Goldstein, P. L. Hayes, W. B. Knighton, H. Oetjen, A. Setyan, H. Stark, R. Thalman, G. Tyndall, R. Washenfelder, E. Waxman, and Q. Zhang
Atmos. Chem. Phys., 14, 6213–6239, https://doi.org/10.5194/acp-14-6213-2014, https://doi.org/10.5194/acp-14-6213-2014, 2014
G. Michalski, S. K. Bhattacharya, and G. Girsch
Atmos. Chem. Phys., 14, 4935–4953, https://doi.org/10.5194/acp-14-4935-2014, https://doi.org/10.5194/acp-14-4935-2014, 2014
X. Zhang, R. H. Schwantes, M. M. Coggon, C. L. Loza, K. A. Schilling, R. C. Flagan, and J. H. Seinfeld
Atmos. Chem. Phys., 14, 1733–1753, https://doi.org/10.5194/acp-14-1733-2014, https://doi.org/10.5194/acp-14-1733-2014, 2014
X. Zhang and J. H. Seinfeld
Atmos. Chem. Phys., 13, 5907–5926, https://doi.org/10.5194/acp-13-5907-2013, https://doi.org/10.5194/acp-13-5907-2013, 2013
Related subject area
Subject: Isotopes | Research Activity: Laboratory Studies | Altitude Range: Troposphere | Science Focus: Chemistry (chemical composition and reactions)
On the potential fingerprint of the Antarctic ozone hole in ice-core nitrate isotopes: a case study based on a South Pole ice core
Temporal variation in 129I and 127I in aerosols from Xi'an, China: influence of East Asian monsoon and heavy haze events
High time-resolved measurement of stable carbon isotope composition in water-soluble organic aerosols: method optimization and a case study during winter haze in eastern China
Dependence between the photochemical age of light aromatic hydrocarbons and the carbon isotope ratios of atmospheric nitrophenols
Evidence for a major missing source in the global chloromethane budget from stable carbon isotopes
Atmospheric Δ17O(NO3−) reveals nocturnal chemistry dominates nitrate production in Beijing haze
Mass spectrometric measurement of hydrogen isotope fractionation for the reactions of chloromethane with OH and Cl
Stable carbon isotope ratios of ambient aromatic volatile organic compounds
Kinetic isotope effects of 12CH3D + OH and 13CH3D + OH from 278 to 313 K
Investigation of post-depositional processing of nitrate in East Antarctic snow: isotopic constraints on photolytic loss, re-oxidation, and source inputs
Chlorine isotope composition in chlorofluorocarbons CFC-11, CFC-12 and CFC-113 in firn, stratospheric and tropospheric air
NOx cycle and the tropospheric ozone isotope anomaly: an experimental investigation
Fractionation of sulfur isotopes during heterogeneous oxidation of SO2 on sea salt aerosol: a new tool to investigate non-sea salt sulfate production in the marine boundary layer
Sulfur isotope fractionation during oxidation of sulfur dioxide: gas-phase oxidation by OH radicals and aqueous oxidation by H2O2, O3 and iron catalysis
Molecular hydrogen (H2) emissions and their isotopic signatures (H/D) from a motor vehicle: implications on atmospheric H2
Isotope effect in the formation of H2 from H2CO studied at the atmospheric simulation chamber SAPHIR
Pressure dependence of the deuterium isotope effect in the photolysis of formaldehyde by ultraviolet light
Yanzhi Cao, Zhuang Jiang, Becky Alexander, Jihong Cole-Dai, Joel Savarino, Joseph Erbland, and Lei Geng
Atmos. Chem. Phys., 22, 13407–13422, https://doi.org/10.5194/acp-22-13407-2022, https://doi.org/10.5194/acp-22-13407-2022, 2022
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We investigate the potential of ice-core preserved nitrate isotopes as proxies of stratospheric ozone variability by measuring nitrate isotopes in a shallow ice core from the South Pole. The large variability in the snow accumulation rate and its slight increase after the 1970s masked any signals caused by the ozone hole. Moreover, the nitrate oxygen isotope decrease may reflect changes in the atmospheric oxidation environment in the Southern Ocean.
Luyuan Zhang, Xiaolin Hou, Sheng Xu, Tian Feng, Peng Cheng, Yunchong Fu, and Ning Chen
Atmos. Chem. Phys., 20, 2623–2635, https://doi.org/10.5194/acp-20-2623-2020, https://doi.org/10.5194/acp-20-2623-2020, 2020
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To trace the long-range transport of air pollutants and understand the atmospheric effect of iodine, the daily-resolution temporal variations of 129I and 127I in aerosols from a monsoonal city indicate the East Asian monsoon and fossil fuel combustion plays crucial roles on transport of 129I from Europe to East Asia and on elevated 127I concentrations. Through linking iodine isotopes with five major air pollutants, this study proposes the possible role of iodine in urban air pollution.
Wenqi Zhang, Yan-Lin Zhang, Fang Cao, Yankun Xiang, Yuanyuan Zhang, Mengying Bao, Xiaoyan Liu, and Yu-Chi Lin
Atmos. Chem. Phys., 19, 11071–11087, https://doi.org/10.5194/acp-19-11071-2019, https://doi.org/10.5194/acp-19-11071-2019, 2019
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A novel method to determine the concentration and the isotopes of WSOC in aerosols is established and applied in the analysis of a severe haze in eastern China. The results show that the studied site is affected by the photochemical aging, biomass burning and dust aerosols in different episodes during the sampling period. The analysis of WSOC and its isotopes offers a great potential to better understand the source emission, the atmospheric aging and the secondary production of WSOC.
Marina Saccon, Anna Kornilova, Lin Huang, and Jochen Rudolph
Atmos. Chem. Phys., 19, 5495–5509, https://doi.org/10.5194/acp-19-5495-2019, https://doi.org/10.5194/acp-19-5495-2019, 2019
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As compound are emitted into the atmosphere, they can undergo chemical reactions to produce secondary products. This paper investigates the relations of compounds' unique chemical characteristics to the processes that formed them from emissions in the atmosphere. A model is applied to help with this investigation. The complexity of the atmosphere, including mixing of air masses and variability in precursor reactivity, is taken into consideration, and results are presented.
Enno Bahlmann, Frank Keppler, Julian Wittmer, Markus Greule, Heinz Friedrich Schöler, Richard Seifert, and Cornelius Zetzsch
Atmos. Chem. Phys., 19, 1703–1719, https://doi.org/10.5194/acp-19-1703-2019, https://doi.org/10.5194/acp-19-1703-2019, 2019
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Chloromethane is the most important natural carrier of chlorine to the stratosphere. From a newly determined carbon isotope effect of −11.2 ‰ for the tropospheric loss of CH3Cl we derive a tropical rainforest CH3Cl source of 670 ± 200 Gg a−1, 60 % smaller than previous estimates. A revision of previous bottom-up estimates using above-ground biomass instead of rainforest area strongly supports this lower estimate. Our results suggest a large unknown tropical value of 1530 ± 200 Gg a−1.
Pengzhen He, Zhouqing Xie, Xiyuan Chi, Xiawei Yu, Shidong Fan, Hui Kang, Cheng Liu, and Haicong Zhan
Atmos. Chem. Phys., 18, 14465–14476, https://doi.org/10.5194/acp-18-14465-2018, https://doi.org/10.5194/acp-18-14465-2018, 2018
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We present the first observations of the oxygen-17 excess of atmospheric nitrate (Δ17O(NO−3)) collected in Beijing haze to reveal the relative importance of different nitrate formation pathways. We found that nocturnal pathways (N2O5 + H2O/Cl– and NO3 + HC) dominated nitrate production during polluted days (PM2.5 ≥ 75 μg m–3), with a mean possible fraction of 56–97 %.
Frank Keppler, Enno Bahlmann, Markus Greule, Heinz Friedrich Schöler, Julian Wittmer, and Cornelius Zetzsch
Atmos. Chem. Phys., 18, 6625–6635, https://doi.org/10.5194/acp-18-6625-2018, https://doi.org/10.5194/acp-18-6625-2018, 2018
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Chloromethane is involved in stratospheric ozone depletion, but detailed knowledge of its global budget is missing. In this study stable hydrogen isotope analyses were performed to investigate the dominant loss process for atmospheric chloromethane with photochemically produced hydroxyl radicals. The findings might have significant implications for the use of stable isotope signatures in elucidation of global chloromethane cycling.
Anna Kornilova, Lin Huang, Marina Saccon, and Jochen Rudolph
Atmos. Chem. Phys., 16, 11755–11772, https://doi.org/10.5194/acp-16-11755-2016, https://doi.org/10.5194/acp-16-11755-2016, 2016
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The photochemical oxidation of organic compounds in the atmosphere results in the formation of important secondary pollutants such as ozone and fine particles. The extent of oxidation the organic compounds have been subjected too since there emissions is essential is key for understanding the formation of secondary pollutants. This paper demonstrates that measurements of the carbon isotope ratios allow determining the extent of photochemical processing for individual compounds.
L. M. T. Joelsson, J. A. Schmidt, E. J. K. Nilsson, T. Blunier, D. W. T. Griffith, S. Ono, and M. S. Johnson
Atmos. Chem. Phys., 16, 4439–4449, https://doi.org/10.5194/acp-16-4439-2016, https://doi.org/10.5194/acp-16-4439-2016, 2016
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We present experimental kinetic isotope effects (KIE) for the OH oxidation of CH3D and 13CH3D and their temperature dependence. Our determination of the 13CH3D + OH KIE is novel and we find no "clumped" isotope effect within the experimental uncertainty.
G. Shi, A. M. Buffen, M. G. Hastings, C. Li, H. Ma, Y. Li, B. Sun, C. An, and S. Jiang
Atmos. Chem. Phys., 15, 9435–9453, https://doi.org/10.5194/acp-15-9435-2015, https://doi.org/10.5194/acp-15-9435-2015, 2015
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We evaluate isotopic composition of NO3- in different environments across East Antarctica. At high snow accumulation sites, isotopic ratios are suggestive of preservation of NO3- deposition. At low accumulation sites, isotopes are sensitive to both the loss of NO3- due to photolysis and secondary formation of NO3- within the snow. The imprint of post-depositional alteration is not uniform with depth, making it difficult to predict the isotopic composition at depth from near-surface data alone.
S. J. Allin, J. C. Laube, E. Witrant, J. Kaiser, E. McKenna, P. Dennis, R. Mulvaney, E. Capron, P. Martinerie, T. Röckmann, T. Blunier, J. Schwander, P. J. Fraser, R. L. Langenfelds, and W. T. Sturges
Atmos. Chem. Phys., 15, 6867–6877, https://doi.org/10.5194/acp-15-6867-2015, https://doi.org/10.5194/acp-15-6867-2015, 2015
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Stratospheric ozone protects life on Earth from harmful UV-B radiation. Chlorofluorocarbons (CFCs) are man-made compounds which act to destroy this barrier.
This paper presents (1) the first measurements of the stratospheric δ(37Cl) of CFCs -11 and -113; (2) the first quantification of long-term trends in the tropospheric δ(37Cl) of CFCs -11, -12 and -113.
This study provides a better understanding of source and sink processes associated with these destructive compounds.
G. Michalski, S. K. Bhattacharya, and G. Girsch
Atmos. Chem. Phys., 14, 4935–4953, https://doi.org/10.5194/acp-14-4935-2014, https://doi.org/10.5194/acp-14-4935-2014, 2014
E. Harris, B. Sinha, P. Hoppe, S. Foley, and S. Borrmann
Atmos. Chem. Phys., 12, 4619–4631, https://doi.org/10.5194/acp-12-4619-2012, https://doi.org/10.5194/acp-12-4619-2012, 2012
E. Harris, B. Sinha, P. Hoppe, J. N. Crowley, S. Ono, and S. Foley
Atmos. Chem. Phys., 12, 407–423, https://doi.org/10.5194/acp-12-407-2012, https://doi.org/10.5194/acp-12-407-2012, 2012
M. K. Vollmer, S. Walter, S. W. Bond, P. Soltic, and T. Röckmann
Atmos. Chem. Phys., 10, 5707–5718, https://doi.org/10.5194/acp-10-5707-2010, https://doi.org/10.5194/acp-10-5707-2010, 2010
T. Röckmann, S. Walter, B. Bohn, R. Wegener, H. Spahn, T. Brauers, R. Tillmann, E. Schlosser, R. Koppmann, and F. Rohrer
Atmos. Chem. Phys., 10, 5343–5357, https://doi.org/10.5194/acp-10-5343-2010, https://doi.org/10.5194/acp-10-5343-2010, 2010
E. J. K. Nilsson, V. F. Andersen, H. Skov, and M. S. Johnson
Atmos. Chem. Phys., 10, 3455–3462, https://doi.org/10.5194/acp-10-3455-2010, https://doi.org/10.5194/acp-10-3455-2010, 2010
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Short summary
Nitrogen isotopic compositions of atmospheric reactive nitrogen are widely used to infer their sources. However, the reactions between NO and NO2 strongly impact their isotopes, which was not well understood. We conducted a series of experiments in an atmospheric simulation chamber to determine the isotopic effects of (1) direct isotopic exchange between NO and NO2 and (2) the isotopic fractionations during NOx photochemistry, then developed an equation to quantify the overall isotopic effect.
Nitrogen isotopic compositions of atmospheric reactive nitrogen are widely used to infer their...
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