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The Impact of the Chemical Production of Methyl Nitrate from the NO+ CH3O2 Reaction on the Global Distributions of Alkyl Nitrates, Nitrogen Oxides and Tropospheric Ozone: a Global

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The Impact of the Chemical Production of Methyl Nitrate from the NO+ CH3O2 Reaction on the Global Distributions of Alkyl Nitrates, Nitrogen Oxides and Tropospheric Ozone: a Global Open Access Atmos. Chem. Phys., 14, 2363–2382, 2014 Atmospheric www.atmos-chem-phys.net/14/2363/2014/ doi:10.5194/acp-14-2363-2014 Chemistry © Author(s) 2014. CC Attribution 3.0 License. and Physics The impact of the chemical production of methyl nitrate from the NO + CH3O2 reaction on the global distributions of alkyl nitrates, nitrogen oxides and tropospheric ozone: a global modelling study J. E. Williams1, G. Le Bras2, A. Kukui3, H. Ziereis4, and C. A. M. Brenninkmeijer5 1Royal Netherlands Meteorological Institute, De Bilt, the Netherlands 2Institut de Combustion, Aérothermique, Réactivité et Environnement, CNRS, Orléans, France 3Laboratoire de Physique et Chimie de l’Environnement et de l’Espace, CNRS, Orléans, France 4DLR, Oberpfaffenhofen, Germany 5Max Planck Institute for Chemistry, Atmospheric Chemistry, Mainz, Germany Correspondence to: J. E. Williams ([email protected]) Received: 28 April 2013 – Published in Atmos. Chem. Phys. Discuss.: 2 August 2013 Revised: 9 December 2013 – Accepted: 9 January 2014 – Published: 7 March 2014 Abstract. The formation, abundance and distribution of or- tions in the free troposphere and underestimations in the up- ganic nitrates are relevant for determining the production per troposphere across a wide range of latitudes and longi- efficiency and resident mixing ratios of tropospheric ozone tudes when compared against data from measurement cam- (O3) on both regional and global scales. Here we investigate paigns. This suggests either a missing transport pathway or the effect of applying the recently measured direct chem- source/sink term, although measurements show significant ical production of methyl nitrate (CH3ONO2) during NOx variability in resident mixing ratios at high altitudes at global recycling involving the methyl-peroxy radical on the global scale. For the vertical profile of RONO2, TM5 performs bet- tropospheric distribution of CH3ONO2 and the perturbations ter at tropical latitudes than at mid-latitudes, with similar fea- introduced towards tropospheric NOx and O3 using the TM5 tures in the comparisons to those for CH3ONO2. Compar- global chemistry transport model. By comparisons against isons of CH3ONO2 with a wide range of surface measure- numerous observations, we show that the global surface dis- ments shows that further constraints are necessary regard- tribution of CH3ONO2 can be largely explained by intro- ing the variability in the deposition terms for different land ducing the chemical production mechanism using a branch- surfaces in order to improve on the comparisons presented ing ratio of 0.3 %, when assuming a direct oceanic emission here. For total reactive nitrogen (NOy) ∼ 20 % originates source of ∼ 0.15 Tg N yr−1. On a global scale, the chemi- from alkyl nitrates in the tropics and subtropics, where the −1 cal production of CH3ONO2 converts 1 Tg N yr from ni- introduction of both direct oceanic emissions and the chemi- trogen oxide for this branching ratio. The resident mixing cal formation mechanism of CH3ONO2 only makes a ∼ 5 % ratios of CH3ONO2 are found to be highly sensitive to the contribution to the total alkyl nitrate content in the upper tro- dry deposition velocity that is prescribed, where more than posphere when compared with aircraft observations. We find 50 % of the direct oceanic emission is lost near the source that the increases in tropospheric O3 that occur due oxida- regions, thereby mitigating the subsequent effects due to tion of CH3ONO2 originating from direct oceanic emission long-range and convective transport out of the source re- is negated when accounting for the chemical formation of gion. For the higher alkyl nitrates (RONO2) we find im- CH3ONO2, meaning that the impact of such oceanic emis- provements in the simulated distribution near the surface in sions on atmospheric lifetimes becomes marginal when a the tropics (10◦ S–10◦ N) when introducing direct oceanic branching ratio of 0.3 % is adopted. emissions equal to ∼ 0.17 Tg N yr−1 . In terms of the ver- tical profile of CH3ONO2, there are persistent overestima- Published by Copernicus Publications on behalf of the European Geosciences Union. 2364 J. E. Williams et al.: A global modelling study 1 Introduction the direct formation of HNO3 from Reaction (1), where the branching ratio depends on pressure, temperature and rela- The chemical production of tropospheric ozone (O3) is crit- tive humidity (Butkovskaya et al., 2005, 2007). This has led ically dependent on the recycling efficiency of NO to NO2 to a number of different global modelling studies associated involving peroxy radicals (Atkinson, 2000). The most abun- with studying the impact of this branching ratio on tropo- dant types of peroxy-radicals (RO2) in the troposphere are spheric composition (Cariolle et al., 2009; Sovde et al., 2011; the hydro peroxy (HO2) and methyl peroxy (CH3O2) rad- Gottschaldt et al., 2013; Boxe et al., 2012). The subsequent icals, which are predominantly formed during the photoly- reduction in the recycling efficiency of NO reduces the pro- sis of chemical precursors such as formaldehyde (HCHO), duction of tropospheric O3, which lowers oxidative capacity. and via oxidation of carbon monoxide (CO) and methane However, some ambiguity still exists as to the catalytic ef- (CH4) during recycling of OH radicals. Once formed in Re- fects of water vapour on the branching ratio (Butkovskaya actions (R1)–(R3), NO2 is rapidly photolysed, producing tro- et al., 2009) meaning that the direct formation of HNO3 is pospheric ozone (O3) by Reactions (R4) and (R5): typically not included in chemical mechanisms employed in large-scale chemistry transport models (CTMs) nor cur- + → + NO HO2 NO2 OH, (R1) rently included in the recommendations (e.g. Sander et al., 2011) due to the lack of an independent measurement for NO + CH O (+O ) → NO + HCHO + HO , (R2) 3 2 2 2 2 this branching ratio. Using the same technique, Butkovskaya et al. (2012) NO + RO → NO + RO, (R3) 2 2 recently detected the direct formation of methyl nitrate 3 (CH3ONO2) from Reaction (2). The branching ratio (Reac- NO2+hv→ NO + O P, (R4) tion 10) inferred for tropospheric conditions is 1.0 ± 0.7 %, 3 and it has a weak temperature and pressure dependence: O P + O2 + M → O3 + M. (R5) NO + CH3O2 + M → CH3ONO2 + M. (R10) Loss of NO may also occur via the titration of O3 (Reac- tion (6)), which moderates O3 mixing ratios in high NOx en- Results from a recent conceptual modelling study by Farmer vironments: et al. (2011) have suggested that the formation of RONO2 during the conversion of NO to NO2 by RO2 under urban NO + O3 → NO2 + O2 (R6) conditions has the potential to significantly reduce the photo- chemical production of O3. Moreover, RONO2 has also been On a global scale, Reaction (1) is the dominant NOx recy- found to be important for the lifetime of NOx whenever cling mechanism involving RO2; it accounts for ∼ 65 % of the total NOx mixing ratio is lower than 500 ppt (Browne total regeneration of NO2, while Reactions (2) and (3) ac- and Cohen, 2012). Therefore, given the importance of Reac- counting for ∼ 25 % and ∼ 10 %, respectively (see Sect. 5). tion (2) in the remote tropical troposphere in terms of NOx However, Reaction (6) is the major NO-to-NO2 recycling recycling, where the largest amount of CH4 is oxidised (Fiore mechanism, where there is no net contribution towards the et al., 2006), Reaction (10) could have implications for the production of O3 under steady state NOx-O3 conditions, global tropospheric O3 burden. The formation of CH3ONO2 meaning that it acts as a moderating step. from the sequestration of NO2 by the CH3O radical has been The chain length of the free-radical reaction cycle de- invoked as another possible source, but it was considered in- scribed above is determined by the efficiency of the chain significant on a global scale because of the high NO2 mixing termination steps in high NOx environments, mainly Reac- ratios which are necessary (Flocke et al., 1998a). The for- tions (R7)–(R9) below. These lead to the formation of oxi- mation of CH3ONO2 during the decomposition of PAN was dised nitrogen reservoirs: nitric acid (HNO3), peroxy-acetyl also suggested, although this mechanism was later shown to nitrate (PAN) and organic nitrates (RONO2), respectively. be rather inefficient (Orlando et al., 1992) and therefore is not included in this study. NO2 + OH + M → HNO3 + M (R7) Alkyl nitrates contribute significantly to the total reac- tive nitrogen (NO ) budget of the troposphere (e.g. Buhr et NO2 + CH3(O)O2 + M → PAN + M (R8) y al., 1990) but measuring them remains difficult. Nonethe- NO + RO2 + M → RONO2 + M (R9) less they have been measured under a wide range of at- mospheric conditions (e.g. Flocke et al., 1998a, b; Blake Although the individual steps of this reaction cycle have et al., 1999; Swanson et al., 2003; Jones et al., 2011) typ- been studied extensively over the last decades, there is still ically by analysing flask measurements, although in some some uncertainty related to the possibility of long lived ni- instances techniques such as gas chromatography with elec- trogen reservoirs being formed directly during Reactions (1) tron capture (Roberts et al., 1998), gas chromatography/mass and (2). For instance, recent laboratory measurements us- spectroscopy (GC–MS; e.g. Dahl et al., 2005) and ther- ing chemical ionisation mass spectroscopy have revealed mal dissociation/laser-induced fluorescence (TD–LIF; e.g. Atmos. Chem. Phys., 14, 2363–2382, 2014 www.atmos-chem-phys.net/14/2363/2014/ J. E. Williams et al.: A global modelling study 2365 Table 1. (a) Mixing ratios of CH3ONO2 measured at the surface over the last few decades. (b) The range of CH3ONO2 mixing ratios measured in the FT (between 2 and 10 km) during research flights over the last few decades from various measurement campaigns.
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