Ozone production efficiencies of acetone and peroxides in the upper troposphere

HOx concentrations in the upper tropical troposphere can be enhanced by the presence of acetone and the convective injection of peroxides. These enhancements in HOx might be expected to increase ozone production by increasing the rate of the HO2+NO reaction. We show however that the convective enhancements of hydrogen peroxide (H2O2) and methyl hydroperoxide (CH3OOH) above steady state during the PEM West B campaign were largely restricted to air parcels of marine boundary layer origin in which the mean NO concentration was 8 pptv. The ozone production efficiencies of the two peroxides at such low NO concentrations are very small. Their impact on the ozone budget of the upper tropical troposphere during PEM West B was therefore probably modest. Unlike the peroxides, acetone in the upper tropical troposphere during PEM West B exhibited a positive correlation with NO. It also has a much larger ozone production efficiency than either H2O2 or CH3OOH. It therefore has a much greater potential for significantly increasing ozone production rates in the upper tropical troposphere

OH, HO_2, NO in two biomass burning plumes: Sources of HO_x and implications for ozone production

The ER-2 made two descents through upper tropospheric biomass burning plumes during ASHOE/MAESA. HO_x (= OH + HO_2) concentrations are largely self-limited outside the plumes, but become progressively more limited by reactions with NO_x (= NO + NO_2) at the higher NO_x concentrations inside the plumes. Sources of HO_x in addition to H_(2)O and CH_4 oxidation are required to balance the known HOx sinks both in the plumes and in the background upper troposphere. HO_x concentrations were consistently underestimated by a model constrained by observed NO_x concentrations. The size of the model underestimate is reduced when acetone photolysis is included. Models which do not include the additional HO_x sources required to balance the HO_x budget are likely to underestimate ozone production rates

Modelling the relationship between liquid water content and cloud droplet number concentration observed in low clouds in the summer Arctic and its radiative effects

Low clouds persist in the summer Arctic with important consequences for the radiation budget. In this study, we simulate the linear relationship between liquid water content (LWC) and cloud droplet number concentration (CDNC) observed during an aircraft campaign based out of Resolute Bay, Canada, conducted as part of the Network on Climate and Aerosols: Addressing Key Uncertainties in Remote Canadian Environments study in July 2014. Using a single-column model, we find that autoconversion can explain the observed linear relationship between LWC and CDNC. Of the three autoconversion schemes we examined, the scheme using continuous drizzle (Khairoutdinov and Kogan, 2000) appears to best reproduce the observed linearity in the tenuous cloud regime (Mauritsen et al., 2011), while a scheme with a threshold for rain (Liu and Daum, 2004) best reproduces the linearity at higher CDNC. An offline version of the radiative transfer model used in the Canadian Atmospheric Model version 4.3 is used to compare the radiative effects of the modelled and observed clouds. We find that there is no significant difference in the upward longwave cloud radiative effect at the top of the atmosphere from the three autoconversion schemes (p=0.05) but that all three schemes differ at p=0.05 from the calculations based on observations. In contrast, the downward longwave and shortwave cloud radiative effect at the surface for the Wood (2005b) and Khairoutdinov and Kogan (2000) schemes do not differ significantly (p=0.05) from the observation-based radiative calculations, while the Liu and Daum (2004) scheme differs significantly from the observation-based calculation for the downward shortwave but not the downward longwave fluxes.This research has been supported by the Natural Sciences and Engineering Research Council of Canada (Discovery Grants RGPIN-2014-05173 and RGPIN 155649) and the Marine Environmental Observation, Prediction and Response Network (MEOPAR), which is a federally funded Networks of Centres of Excellence (NCE) (EC1-RC-DAL).Peer ReviewedPostprint (published version

On the relative role of convection, chemistry, and transport over the South Pacific Convergence Zone during PEM-Tropics B: A case study

A mesoscale 3D model (Meso‐NH) is used to assess the relative importance of convection (transport and scavenging), chemistry, and advection in the vertical redistribution of HOx and their precursors in the upper tropical troposphere. The study is focused on marine deep convection over the South Pacific Convergence Zone (SPCZ) during the PEM‐Tropics B Flight 10 aircraft mission. The model reproduces well the HOx mixing ratios. Vertical variations and the contrast between north and south of the SPCZ for O3 are captured. Convection uplifted O3‐poor air at higher altitude, creating a minimum in the 9–12 km region, in both modeled and observed profiles. The model captured 60% of the observed HCHO variance but fails to reproduce a peak of HCHO mixing ratio at 300 hPa sampled during the northern spirals. Simulated HCHO mixing ratios underestimate observations in the marine boundary layer. In the model, convection is not an efficient process to increase upper tropospheric HCHO, and HCHO is unlikely to serve as a primary source of HOx. Convection plays an important role in the vertical distribution of CH3OOH with efficient vertical transport from the boundary layer to the 10–15 km region where it can act as a primary source of HOx. The SPCZ region acts as a barrier to mixing of tropical and subtropical air at the surface and at high altitudes (above 250 hPa). The 400–270 hPa region over the convergence zone was more permeable, allowing subtropical air masses from the Southern Hemisphere to mix with tropical air from NE of the SPCZ and to be entrained in the SPCZ‐related convection. In this altitude range, exchange of subtropical and tropical air also occurs via airflow, bypassing the convective region SW and proceeding toward the north of the SPCZ

Tropical Convective Outflow and Near Surface Equivalent Potential Temperatures

We use clear sky heating rates to show that convective outflow in the tropics decreases rapidly with height between the 350 K and 360 K potential temperature surfaces (or between roughly 13 and 15 km). There is also a rapid fall-off in the pseudoequivalent potential temperature probability distribution of near surface air parcels between 350 K and 360 K. This suggests that the vertical variation of convective outflow in the upper tropical troposphere is to a large degree determined by the distribution of sub cloud layer entropy

Space-Based Constraints on the Production of Nitric Oxide by Lightning

.We interpret observations of trace-gases from three satellite platforms to provide top-down constraints on the production of NO by lightning. The space-based observations are tropospheric NO2 columns from SCIAMACHY, tropospheric O3 columns from OMI and MLS, and upper tropospheric HNO3 from ACE-FTS. A global chemical transport model (GEOS-Chem) is used to identify locations and time periods in which lightning would be expected to dominate the trace gas observations. The satellite observations are sampled at those locations and time periods. All three observations exhibit a maximum in the tropical Atlantic region and a minimum in the tropical Pacific. This wave-1 pattern is driven by injection of lightning NO into the upper troposphere over the tropical continents, followed by photochemical production of NO2, HNO3, and O3 during transport. Lightning produces a broad enhancement over the tropical Atlantic and Africa of 2-6 x 10(exp 14) molecules NO2/sq cm, 4 x 10(exp 17) molecules O3/sq cm (15 Dobson Units), and 125 pptv of upper tropospheric HNO3. The lightning background is 25-50% weaker over the tropical Pacific. A global source of 6+/-2 Tg N/yr from lightning in the model best represents the satellite observations of tropospheric NO2, O3, and HNO3

Improving Statistical Downscaling of General Circulation Models

We present a new method for the statistical downscaling of coarse-resolution General Circulation Model (GCM) fields to predict local climate change. Most atmospheric variables have strong seasonal cycles. We show that the prediction of the non-seasonal variability of maximum and minimum daily surface temperature is improved if the seasonal cycle is removed prior to the statistical analysis. The new method consists of three major steps. First, the average seasonal cycles of both predictands and predictors are removed. Second, a principal component-based multiple linear regression model between the deseasonalized predictands and predictors is developed and validated. Finally, the regression is used to make projections of future changes in maximum and minimum daily surface temperature at Shearwater, Nova Scotia. This projection is made using the local grid-scale variables of the Canadian General Circulation Model Version 3 (CGCM3) climate model as predictors. Our statistical downscaling method indicates significant skill in predicting the observed distribution of temperature using GCM predictors. Projections suggest minimum and maximum temperatures at Shearwater will be up to about five degrees warmer by 2100 under the current “business-as-usual” scenario. RÉSUMÉ [Traduit par la rédaction] Nous présentons une nouvelle méthode pour la réduction d'échelle statistique des champs des modèles de circulation générale (MCG) à faible résolution pour prévoir les changements du climat local. La plupart des variables atmosphériques ont des cycles saisonniers bien marqués. Nous démontrons que la prédiction de la variabilité non saisonnière de la température de surface quotidienne minimum et maximum est meilleure si on retranche le cycle saisonnier avant de procéder à l'analyse statistique. Voici les trois grandes étapes de cette nouvelle méthode. D'abord, nous retirons les cycles saisonniers moyens des prédictants et des prédicteurs. Ensuite, nous concevons et validons un modèle de régression linéaire multiple sur composantes principales entre les prédictants et les prédicteurs désaisonnalisés. Enfin, nous nous servons de la régression afin d'établir des projections pour les changements à venir dans la température de surface quotidienne minimum et maximum à Shearwater en Nouvelle-Écosse. Cette projection est établie au moyen des variables locales à l'échelle du maillage de la troisième version du modèle canadien de circulation générale (MCCG3). Notre méthode de réduction d'échelle statistique se révèle très efficace pour prédire la répartition observée de la température au moyen des prédicteurs du MCG. D'après les projections, les températures minimum et maximum à Shearwater connaîtront une augmentation d'environ cinq degrés d'ici 2100 dans le scénario actuel de type « statu quo »

Sources of upper tropospheric HO_x over the South Pacific Convergence zone : A case study.

A zero-dimensional (0-D) model has been applied to study the sources of hydrogen oxide radicals (HOx = HO2 + OH) in the tropical upper troposphere during the Pacific Exploratory Mission in the tropics (PEM-Tropics B) aircraft mission over the South Pacific in March–April 1999. Observations made across the Southern Pacific Convergence Zone (SPCZ) and the southern branch of the Intertropical Convergence Zone (ITCZ) provided the opportunity to contrast the relative contributions of different sources of HOx, in a nitrogen oxide radical (NOx)-limited regime, in relatively pristine tropical air. The primary sources of HOx vary significantly along the flight track, in correlation with the supply of water vapor. The latitudinal variation of HOx sources is found to be controlled also by the levels of NOx and primary HOx production rates P(HOx). Budget calculations in the 8- to 12-km altitude range show that the reaction O(1D) + H2O is a major HOx source in the cloud region traversed by the aircraft, including SPCZ and the southern branch of the ITCZ. Production from acetone becomes significant in drier region south of 20°S and can become dominant where water vapor mixing ratios lie under 200 ppmv. Over the SPCZ region, in the cloud outflow, CH3OOH transported by convection accounts for 22% to 64% of the total primary source. Oxidation of methane amplifies the primary HOx source by 1–1.8 in the dry regions