Precipitation of salts in freezing seawater and ozone depletion events: a status report

• Published in: Atmospheric Chemistry and Physics
• Main Authors: Morin, Samuel, Marion, G., Von Glasow, R., Voisin, D., Bouchez, J., Savarino, J.
• Other Authors: Météo France, Thermodynamique et Energétique des fluides complexes (TEFC), Université de Pau et des Pays de l'Adour (UPPA)-TOTAL SA-Centre National de la Recherche Scientifique (CNRS), Institute of Environmental Physics Heidelberg (IUP), Universität Heidelberg Heidelberg, Laboratoire de glaciologie et géophysique de l'environnement (LGGE), Centre National de la Recherche Scientifique (CNRS)-Institut national des sciences de l'Univers (INSU - CNRS)-Observatoire des Sciences de l'Univers de Grenoble (OSUG), Université Joseph Fourier - Grenoble 1 (UJF)-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 Joseph Fourier - Grenoble 1 (UJF)-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), Institut de Physique du Globe de Paris (IPGP), Université Pierre et Marie Curie - Paris 6 (UPMC)-Institut national des sciences de l'Univers (INSU - CNRS)-IPG PARIS-Université Paris Diderot - Paris 7 (UPD7)-Université de La Réunion (UR)-Centre National de la Recherche Scientifique (CNRS)
• Format: Article in Journal/Newspaper
• Language: English
• Published: HAL CCSD 2008
• Subjects: [SDU.OCEAN]Sciences of the Universe [physics]/Ocean; Atmosphere; [SDU.STU.GC]Sciences of the Universe [physics]/Earth Sciences/Geochemistry; [SDU.STU.GL]Sciences of the Universe [physics]/Earth Sciences/Glaciology; Antarctic; Antarc*
• Online Access: https://hal.archives-ouvertes.fr/hal-02133306; https://hal.archives-ouvertes.fr/hal-02133306/document; https://hal.archives-ouvertes.fr/hal-02133306/file/acp-8-7317-2008.pdf; https://doi.org/10.5194/ACP-8-7317-2008

International audience In springtime, the polar marine boundary layer exhibits drastic ozone depletion events (ODEs), associated with elevated bromine oxide (BrO) mixing ratios. The current interpretation of this peculiar chemistry requires the existence of acid and bromide-enriched surfaces to heterogeneously promote and sustain ODEs. Sander et al. (2006) have proposed that calcium carbonate (CaCO 3) precipitation in any seawater-derived medium could potentially decrease its alkalinity, making it easier for atmospheric acids such as HNO 3 and H 2 SO 4 to acidify it. We performed simulations using the state-of-the-art FREZCHEM model, capable of handling the thermodynamics of concentrated electrolyte solutions, to try to reproduce their results, and found that when ikaite (CaCO 3 ·6H 2 O) rather than calcite (CaCO 3) precipitates , there is no such effect on alkalinity. Given that ikaite has recently been identified in Antarctic brines (Dieck-mann et al., 2008), our results show that great caution should be exercised when using the results of Sander et al. (2006), and reveal the urgent need of laboratory investigations on the actual link(s) between bromine activation and the pH of the surfaces on which it is supposed to take place at subzero temperature. In addition, the evolution of the Cl/Br ratio in the brine during freezing was computed using FREZCHEM, taking into account Br substitutions in Cl-containing salts.