Changes to the chemical state of the northern hemisphere atmosphere during the second half of the twentieth century

• Main Authors: Newland, Mike, Martinerie, Patricia, Witrant, Emmanuel, Helmig, Detlev, Worton, David, Hogan, Chris, Sturges, William, Reeves, Claire
• Other Authors: University of East Anglia Norwich (UEA), Observatoire des Sciences de l'Univers de Grenoble (OSUG ), 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 ), GIPSA - Systèmes linéaires et robustesse (GIPSA-SLR), Département Automatique (GIPSA-DA), Grenoble Images Parole Signal Automatique (GIPSA-lab ), Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut National Polytechnique de Grenoble (INPG)-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 Polytechnique de Grenoble (INPG)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes 2016-2019 (UGA 2016-2019 )-Grenoble Images Parole Signal Automatique (GIPSA-lab ), Institut polytechnique de Grenoble - Grenoble Institute of Technology (Grenoble INP )-Institut National Polytechnique de Grenoble (INPG)-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 Polytechnique de Grenoble (INPG)-Centre National de la Recherche Scientifique (CNRS)-Université Grenoble Alpes 2016-2019 (UGA 2016-2019 ), Institute of Arctic Alpine Research University of Colorado Boulder (INSTAAR), University of Colorado Boulder, National Physical Laboratory Teddington (NPL)
• Format: Article in Journal/Newspaper
• Language: English
• Published: HAL CCSD 2016
• Subjects: [SPI.AUTO]Engineering Sciences [physics]/Automatic; Greenland; Human health
• Online Access: https://hal.science/hal-01411413; https://hal.science/hal-01411413/document; https://hal.science/hal-01411413/file/acp-2016-927.pdf; https://doi.org/10.5194/acp-2016-927

International audience Abstract. The NOx (NO and NO2) and HOx (OH and HO2) budgets of the atmosphere exert a major influence on atmospheric composition, controlling removal of primary pollutants and formation of a wide range of secondary products, including ozone, that can influence human health and climate. However, there remain large uncertainties in the changes to these budgets over recent decades. Due to their short atmospheric lifetimes, NOx and HOx are highly variable in space and time, and so the measurements of these species are of limited value for examining long-term, large-scale changes to their budgets. Here, we take an alternative approach by examining long-term atmospheric trends of alkyl nitrates, the production efficiency of which is dependent on the atmospheric [NO] ∕ [HO2] ratio. We derive long-term trends in the alkyl nitrates from measurements in firn air from the NEEM site, Greenland. Their mixing ratios increased by a factor of 3–5 between the 1970s and 1990s. This was followed by a steep decline to the sampling date of 2008. Moreover, we examine how the trends in the alkyl nitrates compare to similarly derived trends in their parent alkanes (i.e. the alkanes which, when oxidised in the presence of NOx, lead to the formation of the alkyl nitrates). The ratios of the alkyl nitrates to their parent alkanes increased from around 1970 to the late 1990s. This is consistent with large changes to the [NO] ∕ [HO2] ratio in the Northern Hemisphere atmosphere during this period. Alternatively, they could represent changes to concentrations of the hydroxyl radical, OH, or to the transport time of the air masses from source regions to the Arctic.