Missing Gas-Phase Source of HONO Inferred from Zeppelin Measurements in the Troposphere

Li, Xin; Rohrer, Franz; Hofzumahaus, A.; Brauers, T.; Häseler, R.; Bohn, Birger; Broch, Sebastian; Fuchs, Hendrik; Gomm, Sebastian; Holland, F.; Jäger, Julia; Kaiser, Jennifer; Keutsch, Frank N.; Lohse, Insa; Lu, Keding; Tillmann, Ralf; Wegener, Robert; Wolfe, G. M.; Mentel, Thomas F.; Kiendler‐Scharr, Astrid; Wahner, Andreas

doi:10.1126/science.1248999

Cited by 183 publications

(201 citation statements)

References 52 publications

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“…Other aspects of chemistry that are often omitted include the full range of peroxy radical cross reactions (incomplete in even the MCM; Saunders et al, 2003); peroxy radical recycling from isoprene oxidation (e.g., Crounse et al, 2011;Peters et al, 2014), which some studies indicate can affect OH levels and VOC lifetimes over low-NO x forested areas (Archibald et al, 2010b(Archibald et al, , 2011Taraborrelli et al, 2012); nitryl chloride (ClNO 2 ), which has been found to be important in oxidative chemistry, particularly in coastal regions (e.g., Osthoff et al, 2008); and nitrous acid (HONO) formation other than from NO + OH (+M), including from other gas phase sources (Bejan et al, 2007: Li et al, 2008Li et al, 2014), bacteria (Oswald et al, 2013), aerosol reactions (Ammann et al, 1998Stemmler et al, 2007) and heterogeneous processes (Zhou et al, 2001;Stemmler et al, 2006;Su et al, 2011;Mao et al, 2013). In general, heterogeneous processes (Ravishankara, 1997;Jacob, 2000) are simulated in most models, although typically only for a few species (e.g., heterogeneous formation of N 2 O 5 and loss of HO 2 ) and with substantial variation in uptake coefficients, which can have notable effects on modeled abundances and chemical budgets (e.g., Evans and Jacob, 2005;Macintyre and Evans, 2010).…”

Section: Chemistrymentioning

confidence: 99%

Tropospheric Ozone Assessment Report: Assessment of global-scale model performance for global and regional ozone distributions, variability, and trends

Young

Naik

Fiore

et al. 2018

Elementa: Science of the Anthropocene

264

274

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The goal of the Tropospheric Ozone Assessment Report (TOAR) is to provide the research community with an up-to-date scientific assessment of tropospheric ozone, from the surface to the tropopause. While a suite of observations provides significant information on the spatial and temporal distribution of tropospheric ozone, observational gaps make it necessary to use global atmospheric chemistry models to synthesize our understanding of the processes and variables that control tropospheric ozone abundance and its variability. Models facilitate the interpretation of the observations and allow us to make projections of future tropospheric ozone and trace gas distributions for different anthropogenic or natural perturbations. This paper assesses the skill of current-generation global atmospheric chemistry models in simulating the observed present-day tropospheric ozone distribution, variability, and trends. Drawing upon the results of recent international multi-model intercomparisons and using a range of model evaluation techniques, we demonstrate that global chemistry models are broadly skillful in capturing the spatio-temporal variations of tropospheric ozone over the seasonal cycle, for extreme pollution episodes, and changes over interannual to decadal periods. However, models are consistently biased high in the northern hemisphere and biased low in the southern hemisphere, throughout the depth of the troposphere, and are unable to replicate particular metrics that define the longer term trends in tropospheric ozone as derived from some background sites. When the models compare unfavorably against observations, we discuss the potential causes of model biases and propose directions for future developments, including improved evaluations that may be able to better diagnose the root cause of the model-observation disparity. Overall, model results should be approached critically, including determining whether the model performance is acceptable for the problem being addressed, whether biases can be tolerated or corrected, whether the model is appropriately constituted, and whether there is a way to satisfactorily quantify the uncertainty.

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Section: Chemistrymentioning

confidence: 99%

Tropospheric Ozone Assessment Report: Assessment of global-scale model performance for global and regional ozone distributions, variability, and trends

Young

Naik

Fiore

et al. 2018

Elementa: Science of the Anthropocene

264

274

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“…Figure 3b shows a time series of the NO and NO 2 observations that has been re-scaled to a smaller range on the y axis so that the relatively higher NO x on 29 and 30 March can be discerned. A recent paper by Li et al (2014) speculates a possible additional gas-phase source of HONO from the reaction of NO 2 with an HO 2 × H 2 O complex. However, as laboratory studies are still required to quantify the efficiency of this mechaAtmos.…”

Section: Atmosmentioning

confidence: 99%

Interactions of bromine, chlorine, and iodine photochemistry during ozone depletions in Barrow, Alaska

et al. 2015

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Abstract. The springtime depletion of tropospheric ozone in the Arctic is known to be caused by active halogen photochemistry resulting from halogen atom precursors emitted from snow, ice, or aerosol surfaces. The role of bromine in driving ozone depletion events (ODEs) has been generally accepted, but much less is known about the role of chlorine radicals in ozone depletion chemistry. While the potential impact of iodine in the High Arctic is more uncertain, there have been indications of active iodine chemistry through observed enhancements in filterable iodide, probable detection of tropospheric IO, and recently, observation of snowpack photochemical production of I 2 . Despite decades of research, significant uncertainty remains regarding the chemical mechanisms associated with the bromine-catalyzed depletion of ozone, as well as the complex interactions that occur in the polar boundary layer due to halogen chemistry. To investigate this, we developed a zero-dimensional photochemical model, constrained with measurements from the 2009 OA-SIS field campaign in Barrow, Alaska. We simulated a 7-day period during late March that included a full ozone depletion event lasting 3 days and subsequent ozone recovery to study the interactions of halogen radicals under these different conditions. In addition, the effects of iodine added to our Base Model were investigated. While bromine atoms were primarily responsible for ODEs, chlorine and iodine were found to enhance the depletion rates and iodine was found to be more efficient per atom at depleting ozone than Br. The interaction between chlorine and bromine is complex, as the presence of chlorine can increase the recycling and production of Br atoms, while also increasing reactive bromine sinks under certain conditions. Chlorine chemistry was also found to have significant impacts on both HO 2 and RO 2 , with organic compounds serving as the primary reaction partner for Cl atoms. The results of this work highlight the need for future studies on the production mechanisms of Br 2 and Cl 2 , as well as on the potential impact of iodine in the High Arctic.

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“…R2b artificially increased the HNO 3 production rate by a factor of 10. The R3 run assumed HONO formation from the reaction HO 2 + NO 2 in the presence of H 2 O proposed by Li et al (2014). The R4 run added heterogeneous loss of HO 2 on the aerosol particle surface.…”

Section: Box Model Simulationsmentioning

confidence: 99%

Diagnosis of Photochemical Ozone Production Rates and Limiting Factors in Continental Outflow Air Masses Reaching Fukue Island, Japan: Ozone-Control Implications

Kanaya

Tanimoto

Yokouchi

et al. 2016

Aerosol Air Qual. Res.

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Asian continental outflow air masses reach western Japan in the springtime, carrying high levels of ozone produced over the Asian continent, and facilitating in-situ production. In this study, in-situ production was highlighted; the rate and limiting factors of net ozone production were diagnosed at Fukue Island, a remote island west of Japan, on 17 days during May-June 2009, when the continental outflow air mass arrived, using an observation-based modeling approach. The average ozone production was estimated to be 6.8 ppb per day. Information on the chemical status of the arriving air mass is important, because it affects how further ozone production in the air mass occurs after precursor addition from Japanese domestic emissions. The main limiting factor of ozone production for such air masses was usually nitrogen oxides (NO x ), suggesting that domestic NO x emission control is important in reducing further ozone production. Volatile organic compounds (VOCs) also increased the ozone production rate, and occasionally (14% of time) became the dominant controlling factor. This analysis implies that the VOC reduction legislation recently enacted by the Japanese government should be effective. VOC-limited conditions occurred particularly when the air mass traveled within 6-8 h, via the Korean Peninsula. The uncertainty in the radical chemistry mechanism governing ozone production had a non-negligible impact, but the main conclusion relevant to policy was not altered. When chain termination was augmented by HO 2 + NO/NO 2 reactions in the presence of H 2 O and by heterogeneous loss of HO 2 on aerosol particle surfaces, as recently verified or hypothesized, the daily ozone production rate decreased by up to 24%, and the fraction of hours when the VOC-limited condition occurred varied from 14% to 13-26%.

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Missing Gas-Phase Source of HONO Inferred from Zeppelin Measurements in the Troposphere

Cited by 183 publications

References 52 publications

Tropospheric Ozone Assessment Report: Assessment of global-scale model performance for global and regional ozone distributions, variability, and trends

Tropospheric Ozone Assessment Report: Assessment of global-scale model performance for global and regional ozone distributions, variability, and trends

Interactions of bromine, chlorine, and iodine photochemistry during ozone depletions in Barrow, Alaska

Diagnosis of Photochemical Ozone Production Rates and Limiting Factors in Continental Outflow Air Masses Reaching Fukue Island, Japan: Ozone-Control Implications

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