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Atmospheric Chemistry of NO₃: Reactions with a Series of Organic

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Atmospheric Chemistry of NO₃: Reactions with a Series of Organic Atmospheric chemistry of NO : reactions with a series of organic and inorganic compounds Li Zhou To cite this version: Li Zhou. Atmospheric chemistry of NO : reactions with a series of organic and inorganic compounds. Other. Université d’Orléans, 2017. English. NNT : 2017ORLE2055. tel-01967629 HAL Id: tel-01967629 https://tel.archives-ouvertes.fr/tel-01967629 Submitted on 1 Jan 2019 HAL is a multi-disciplinary open access L’archive ouverte pluridisciplinaire HAL, est archive for the deposit and dissemination of sci- destinée au dépôt et à la diffusion de documents entific research documents, whether they are pub- scientifiques de niveau recherche, publiés ou non, lished or not. The documents may come from émanant des établissements d’enseignement et de teaching and research institutions in France or recherche français ou étrangers, des laboratoires abroad, or from public or private research centers. publics ou privés. UNIVERSITÉ D’ORLÉANS ÉCOLE DOCTORALE ENERGIE, MATERIAUX, SCIENCES DE LA TERRE ET DE L’UNIVERS ICARE-CNRS ORLEANS THÈSE présentée par : Li ZHOU soutenue le : 15 Décembre 2017 pour obtenir le grade de : Docteur de l’université d’Orléans Discipline/ Spécialité : Chimie et Physique de l’Environment Atmospheric chemistry of NO3 : reactions with a series of organic and inorganic compounds THÈSE dirigée par : Véronique DAËLE Chargée de recherche (HDR) – CNRS-ICARE RAPPORTEURS : Bénédicte PICQUET-VARRAULT Professeure Université Paris Est Créteil / LISA Eric VILLENAVE Professeur Université de Bordeaux ____________________________________________________________________ JURY Bénédicte PICQUET-VARRAULT Professeure - Université Paris Est Créteil / LISA Rapporteur Eric VILLENAVE Professeur - Université de Bordeaux / EPOC Rapporteur A.R. RAVISHANKARA Professeur - Colorado State University-USA Examinateur Coralie SCHOEMAECKER Chargée de Recherche - PC2A - Lille Examinatrice Valéry CATOIRE Professeur - Université d’Orléans/CNRS-LPC2E Examinateur Abdelwahid MELLOUKI Directeur de recherche - CNRS-ICARE Co-Encadrant Véronique DAËLE Chargée de recherche (HDR) - CNRS-ICARE Directrice de thèse Table of Contents Table of Contents Abstract ..................................................................................................................... 5 Chapter I Introduction ............................................................................................. 8 1 The nitrate radical in the atmosphere ................................................................... 8 1.1 Atmospheric sources of NO3 radical ........................................................... 12 1.2 Atmospheric sinks of NO3 radical ............................................................... 14 1.3 Spectroscopy of NO3 ................................................................................... 17 2 Measurement techniques for the nitrate radical (NO3) in the troposphere ........ 18 2.1 Differential Optical Absorption Spectroscopy (DOAS) .............................. 18 2.2 Matrix Isolation Electron Spin Resonance (MI-ESR) ................................. 20 2.3Laser Induced Fluorescence spectroscopy (LIF) .......................................... 21 2.4 Cavity Ring Down Spectroscopy (CRDS) .................................................. 22 2.5 Cavity Enhanced Absorption Spectroscopy (CEAS) .................................. 23 2.6 Chemical Ionization Mass Spectrometry (CIMS) ....................................... 25 2.7 Summary ..................................................................................................... 26 3 The unresolved issues in NO3 radical chemistry ............................................... 27 3.1 Kinetics and mechanisms of NO3 chemical reactions ................................. 28 3.2 Field measurements and model estimation ................................................. 29 3.3 Experimental techniques ............................................................................. 30 4 Motivation and outline of this thesis .................................................................. 30 References ............................................................................................................. 33 Chapter II Experimental system ........................................................................... 43 1 Reactor - indoor smog chamber ......................................................................... 43 2 Instruments ......................................................................................................... 47 2.1 Fourier Transform Infrared Spectroscopy (FTIR) ....................................... 47 2.2 Proton Transfer Reaction-Time of Flight Mass Spectrometry (PTR-ToF-MS) .................................................................................................. 48 2.3 Cavity Ring down Spectroscopy (CRDS) ................................................... 51 2.4 Nitrogen Dioxide (NO2) monitor ................................................................ 55 1 Table of Contents 2.5 Ozone (O3) monitor ..................................................................................... 58 2.6 Formaldehyde (HCHO) analyzer ................................................................ 60 References ............................................................................................................. 62 Chapter III Laboratory studies of the nitrate radical - Reaction of Methacrylate esters with NO3 radicals ................................................................. 66 Abstract ................................................................................................................. 66 1 Introduction ........................................................................................................ 67 2 Experimental system .......................................................................................... 69 2.1 Reactors- Indoor atmospheric simulation chamber ..................................... 69 2.2 Instrumentations .......................................................................................... 71 2.3 Chemicals .................................................................................................... 73 3 Rate coefficients measurement .......................................................................... 74 3.1 Relative rate method .................................................................................... 74 3.2 Rate coefficients via monitoring temporal profiles of NO3/N2O5 loss using CRDS ................................................................................................................. 80 3.3 Error estimation ........................................................................................... 85 3.4 Comparison of rate coefficients obtained from two methods ..................... 88 3.5 Comparison with the kinetic results in literature ......................................... 89 4 Mechanism and Relationship between structure and reactivity of the methacrylate esters ................................................................................................ 91 5 Atmospheric implication .................................................................................... 96 Supporting information ......................................................................................... 99 References ........................................................................................................... 111 Chapter IV Kinetics of the Reactions of NO3 Radical with alkanes ................ 117 Abstract ............................................................................................................... 117 1 Introduction ...................................................................................................... 118 2 Experimental section ........................................................................................ 120 2.1 Experimental system ................................................................................. 120 2.2 Chemicals .................................................................................................. 124 2 Table of Contents 2.3 Kinetic study methods ............................................................................... 126 3 Results and discussion ..................................................................................... 127 3.1 Accounting for impurities and subsequent reactions ................................. 127 3.2 Experimental results .................................................................................. 129 3.3 Error estimation ......................................................................................... 135 3.4 Comparison with the kinetic results in literature ....................................... 141 3.5 Relation between structure and reactivity of alkanes. ............................... 144 4 Conclusions and atmospheric implication ....................................................... 145 Supporting information ....................................................................................... 147 References ........................................................................................................... 162 Chapter V Exploration of minor pathways for the atmospheric removal of N2O, CO and SO2: Reactions with NO3 .............................................................. 168 Abstract ............................................................................................................... 168 1 Introduction
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