Oxygen isotope mass balance of atmospheric nitrate at Dome C, East Antarctica, during the OPALE campaign

International audience Variations in the stable oxygen isotope composition of atmospheric nitrate act as novel tools for studying oxidative processes taking place in the troposphere. They provide both qualitative and quantitative constraints on the pathways determining the fate of atmospheric nitrog...

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Published in:Atmospheric Chemistry and Physics
Main Authors: Savarino, Joël, Vicars, William C., Legrand, Michel, Preunkert, Suzanne, Jourdain, Bruno, Frey, Markus M., Kukui, Alexandre, Caillon, Nicolas, Gil Roca, Jaime
Other Authors: Laboratoire de glaciologie et géophysique de l'environnement (LGGE), Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Observatoire des Sciences de l'Univers de Grenoble (OSUG ), Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut national des sciences de l'Univers (INSU - CNRS)-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Savoie Mont Blanc (USMB Université de Savoie Université de Chambéry )-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes 2016-2019 (UGA 2016-2019 )-Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut national de recherche en sciences et technologies pour l'environnement et l'agriculture (IRSTEA)-Université Savoie Mont Blanc (USMB Université de Savoie Université de Chambéry )-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes 2016-2019 (UGA 2016-2019 ), Université Grenoble Alpes 2016-2019 (UGA 2016-2019 ), Colorado Department of Public Health and Environment, University of Colorado Denver, Institute of Arctic Alpine Research University of Colorado Boulder (INSTAAR), University of Colorado Boulder, British Antarctic Survey (BAS), Natural Environment Research Council (NERC), Laboratoire de Physique et Chimie de l'Environnement et de l'Espace (LPC2E), Observatoire des Sciences de l'Univers en région Centre (OSUC), Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire de Paris, Université Paris sciences et lettres (PSL)-Université Paris sciences et lettres (PSL)-Université d'Orléans (UO)-Centre National de la Recherche Scientifique (CNRS)-Centre National d’Études Spatiales Paris (CNES), TROPO - LATMOS, Laboratoire Atmosphères, Milieux, Observations Spatiales (LATMOS), Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université de Versailles Saint-Quentin-en-Yvelines (UVSQ)-Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS), European Community's Seventh Framework Programme (FP7/2007-2013), INSU (LEFE Programme), Agence Nationale de la Recherche (ANR), IPEV (programme SUNITEDC n° 1011), ANR-05-PGCU-0004,OPALE,Risque d'inondation en ville et évaluation de scénarios(2005), ANR-10-LABX-0056,OSUG@2020,Innovative strategies for observing and modelling natural systems(2010), European Project: 237890,EC:FP7:PEOPLE,FP7-PEOPLE-ITN-2008,INTRAMIF(2009)
Format: Article in Journal/Newspaper
Language:English
Published: HAL CCSD 2016
Subjects:
Online Access:https://hal-insu.archives-ouvertes.fr/insu-01282571
https://hal-insu.archives-ouvertes.fr/insu-01282571/document
https://hal-insu.archives-ouvertes.fr/insu-01282571/file/acp-16-2659-2016.pdf
https://doi.org/10.5194/acp-16-2659-2016
Description
Summary:International audience Variations in the stable oxygen isotope composition of atmospheric nitrate act as novel tools for studying oxidative processes taking place in the troposphere. They provide both qualitative and quantitative constraints on the pathways determining the fate of atmospheric nitrogen oxides (NO + NO 2 = NO x ). The unique and distinctive 17 O excess (Δ 17 O = δ 17 O − 0.52 × δ 18 O) of ozone, which is transferred to NO x via oxidation, is a particularly useful isotopic fingerprint in studies of NO x transformations. Constraining the propagation of 17 O excess within the NO x cycle is critical in polar areas, where there exists the possibility of extending atmospheric investigations to the glacial–interglacial timescale using deep ice core records of nitrate. Here we present measurements of the comprehensive isotopic composition of atmospheric nitrate collected at Dome C (East Antarctic Plateau) during the austral summer of 2011/2012. Nitrate isotope analysis has been here combined for the first time with key precursors involved in nitrate production (NO x , O 3 , OH, HO 2 , RO 2 , etc.) and direct observations of the transferrable Δ 17 O of surface ozone, which was measured at Dome C throughout 2012 using our recently developed analytical approach. Assuming that nitrate is mainly produced in Antarctica in summer through the OH + NO 2 pathway and using concurrent measurements of OH and NO 2 , we calculated a Δ 17 O signature for nitrate on the order of (21–22 ± 3) ‰. These values are lower than the measured values that ranged between 27 and 31 ‰. This discrepancy between expected and observed Δ 17 O(NO 3 − ) values suggests the existence of an unknown process that contributes significantly to the atmospheric nitrate budget over this East Antarctic region. However, systematic errors or false isotopic balance transfer functions are not totally excluded.