Effect of mixed-phase cloud on the chemical budget of trace gases: A modeling approach

International audienceA multiphase cloud chemistry model coupling a detailed chemical reactivity mechanism in gas phase and aqueous phase to a cloud parcel model with a two-moment microphysical scheme has been extended to include ice phase processes. This newly developed model is used to study the influence of the ice phase on HCOOH, HNO3, H2O2 and CH2O in a mixed-phase cloud. Microphysical processes are describing the interactions between the water vapor phase, the liquid phase (cloud and rain water) and the ice phase (pristine ice, snow and graupel) in the cloud and for soluble chemical species, their transfer by mixed-phase microphysical processes has been included. In addition to microphysical transfer between iced hydrometeors, the probable two main processes incorporating soluble chemical species in iced hydrometeors are the retention in ice phase as riming or freezing occurs and the burial in the ice crystal as the crystal grows by vapor diffusion. The model is applied to a cloud event describing a moderate precipitating mixed-phase cloud forming in a continental air mass in winter. The main features of the cloud are described and the evolution of key chemical species as function of time and temperature is discussed. Sensitivity tests are performed: a run without ice to highlight the influence of ice phase on the chemical gas phase composition of the cloud, a run without burial showing that it is a negligible process, a run assuming full retention in ice for all species and a run varying the ice crystal shapes. A detailed analysis of the microphysical rates and chemical rates linked to retention and burial effects show that for this cloud event, the effect of the ice phase on gas phase composition is driven by riming of cloud droplets onto graupels, which leads to retention or not of soluble chemical species in the ice phase. Finally, the impact of crystal geometry on the efficiency of collection is studied together with its impact on the riming of cloud droplets on graupels and also on the retention of chemical species in ice phase

Mixing of dust aerosols into a mesoscale convective system: Generation, filtering and possible feedbacks on ice anvils

International audienceDuring the second Specific Observing Period (SOP) of the African Monsoon Multidisplinary Analyses (AMMA) campaign, several intense mesoscale convective systems (MCS) developed over Niger. An examination of a particular convective storm simulated with a mesoscale model near Banizoumbou, Niger, on 1 July, 2006, shows that this MCS generates a strong emission of dust particles at the leading edge of its density current. A fraction of these dust aerosols are uplifted by the convective core of the system and redistributed by aqueous processes. Aerosol impaction scavenging is the main process by which particles are deposited within the mesoscale convective system. However, small particles (smaller than 1 μm) that are not efficiently scavenged, are able to reach the upper troposphere at a concentration of 6 particles per cm3. This suggests that deep convection over semi-arid regions is able to create its own ice nuclei in high concentrations. This leads to the question: can deep convection over semi-arid regions affect particular ice properties such as ice anvil extension or induce possible feedbacks of dust on precipitation through ice sedimentation

Numerical quantification of sources and phase partitioning of chemical species in cloud: Application to wintertime anthropogenic air masses at the Puy de Dôme station

International audienceThe Model of Multiphase Cloud Chemistry M2C2 has recently been extended to account for nucleation scavenging of aerosol particles in the cloud water chemical composition. This extended version has been applied to multiphase measurements available at the Puy de Dôme station for typical wintertime anthropogenic air masses. The simulated ion concentrations in cloud water are in reasonable agreement with the experimental data. The analysis of the sources of the chemical species in cloud water shows an important contribution from nucleation scavenging of particles which prevails for nitrate, sulphate and ammonium. Moreover, the simulation shows that iron, which comes only from the dissolution of aerosol particles in cloud water, has a significant contribution in the hydroxyl radical production. Finally, the simulated phase partitioning of chemical species in cloud are compared with measurements. Numerical results show an underestimation of interstitial particulate phase fraction with respect to the measurements, which could be due to an overestimation of activated mass by the model. However, the simulated number scavenging efficiency of particles agrees well with the measured value of 40% of total number of aerosol particles activated in cloud droplets. Concerning the origin of chemical species in cloud water, the model reproduces quite well the contribution of gas and aerosol scavenging estimated from measurements. In addition, the simulation provides the contribution of in-cloud chemical reactivity to cloud water concentrations

Molecular composition of clouds: a comparison between samples collected at tropical (Réunion Island, France) and mid-north (Puy de Dôme, France) latitudes

The composition of dissolved organic matter of cloud water has been investigated through non-targeted high-resolution mass spectrometry on only a few samples that were mostly collected in the Northern Hemisphere in the USA, Europe and China. There remains, therefore, a lack of measurements for clouds located in the Southern Hemisphere, under tropical conditions and influenced by forest emissions. As a matter of fact, the comparison of the composition of clouds collected in different locations is challenging since the methodology for the analysis and data treatment is not standardized. In this work, the chemical composition of three samples collected at Réunion Island (REU) during the BIO-MAÏDO field campaign, in the Indian Ocean, with influences from marine, anthropogenic and biogenic (tropical) emissions, is investigated and compared to the chemical composition of samples collected at the Puy de Dôme (PUY) observatory in France. The same methodology of analysis and data treatment was employed, producing a unique dataset for the investigation of the molecular composition of organic matter in cloud water. Besides the analysis of elemental composition, we investigated the carbon oxidation state (OSC) of dissolved organic matter, finding that overall samples collected at PUY are more oxidized than those collected at REU. Molecular formulas were also classified based on stoichiometric elemental ratios, showing the high frequency and abundance of reduced organic compounds, classified as lipids (LipidC), in this matrix, which led to a search for terpene oxidation products in cloud water samples. To better discriminate between samples collected at PUY and REU, statistical analysis (principal component analysis and agglomerative hierarchical clustering) was performed on the ensemble of molecular formulas and their intensities. Samples collected at REU have a different composition from samples collected at PUY, which is mainly linked to different primary sources, the processing of organic matter in cloud water and the influence of different primary emissions at the two locations.</p

Développement d'un modèle de chimie multiphase couplé à un modèle de microphysique quasi-spectral : Application à un événement nuageux échantillonné au Puy de Dôme

Clouds influence the oxidizing capacity of the troposphere and also, the radiative balance of the planet through the multiphase chemical processes which are still poorly understood. The aim of this work was to improve our understanding of the physico-chemical processes inside clouds. For this purpose, a numerical model of multiphase chemistry has been developed and coupled with a microphysical model (Berry and Reinhardt, 1974) based on the gas phase chemistry model of Madronich and Calvert (1990), the chemical mechanism of Jacob (1986), an exhaustive compilation of data from the literature and collaborations with kinetics researchers. In order to perform the necessary link for the understanding of the multiphase chemistry between experimental in situ data and laboratory data, the model in its non coupled version has been applied to a cloudy event sampled at the Puy de Dôme mountain (Voisin et al., 2000). These results show the ability of the model to reproduce generally observed behaviour and to analyse the reactivity of the cloud chemical system (Leriche et al., 2000a). In particular, a new oxidation pathway of S(IV) by pernitric acid into strong acid has been identified. Finally, the coupled model has been applied to the same cloudy event with a academic scenario in order to quantify the influence of the rain formation on the chemical regime previously described. The main results (Leriche et al., 2000b) show that the presence of clouds results in two different effects on the tropospheric chemistry: a direct effect of chemical species scavenging through mass transfer, solubility and reactivity, and an indirect effect through microphysical conversions of cloud water into rainwater which lead to the redistribution of reactive species between interstitial air, cloud water and rainwater.La présence de nuages influence la capacité oxydante de la troposphère, mais aussi le bilan radiatif de la planète notamment à travers les processus liés à la chimie multiphase qui restent mal connus. Le but de ce travail était d'améliorer notre compréhension des processus physico-chimiques au sein des nuages. Pour cela, nous avons développé un modèle numérique de chimie multiphase couplé à un modèle de microphysique (Berry et Reinhardt, 1974), fondé sur le modèle de chimie gazeuse de Madronich et Calvert (1990), le mécanisme réactionnel développé par Jacob (1986), une compilation exhaustive des données de la littérature et des collaborations avec des cinéticiens. Afin d'effectuer le lien nécessaire à la compréhension de la chimie multiphase entre les données de laboratoire et les données de terrain, le modèle dans sa version non couplée a été appliqué dans le cadre d'un événement nuageux échantillonné au Puy de Dôme (Voisin et coll., 2000). Ces résultats montrent en général la capacité du modèle à reproduire les comportements observés et sa capacité d'analyse de la réactivité du système chimique nuageux (Leriche et coll., 2000a). Notamment, une nouvelle voie réactionnelle d'oxydation du S(IV) par l'acide pernitrique en acide fort a été mise en évidence. Finalement, le modèle couplé chimie/microphysique a été appliqué au même événement nuageux sur la base d'un scénario académique afin de quantifier l'influence de la formation de la pluie sur le régime chimique précédemment étudié. Les résultats principaux obtenus (Leriche et coll., 2000b) montrent que la présence de nuages exerce deux effets différents sur la chimie troposphérique : un effet direct de lessivage des espèces chimiques par transfert de masse, solubilité et réactivité, et un effet indirect lié aux transferts microphysiques de l'eau nuageuse en eau précipitante et à la redistribution d'espèces réactives entre l'air interstitiel, l'eau nuageuse et l'eau précipitante

Modeling study of strong acids formation and partitioning in a polluted cloud during wintertime

International audienceA multiphase chemistry model coupled with a quasi-spectral microphysical model has been applied to measurements from the European Cloud Ice Mountain Experiment campaign to quantify the formation of the strong acids nitrate and sulfate and to evaluate the role of microphysical processes in redistributing reactive species among the different phases (gas versus cloud and/or rain). Significant formation of nitrate and sulfate are found to be due to the reaction of pernitric acid with the sulfite ion. Moreover, pernitric acid, because of its equilibrium in the gas phase and its high solubility, is always available both in cloud water and in rainwater via mass transfer from the gas phase. The sulfite ion comes from the mass transfer from the gas phase of sulfur dioxide in cloud water. When rain formation begins, it is efficiently transferred to the rainwater by collision/coalescence processes. This leads to an enhancement in strong acid production when microphysics is activated in the model. Modeled results have been compared with experimental data in an effort to retrieve a behavior law related to the partitioning between the gas and aqueous phases of the cloud. In particular, when collision/coalescence processes are considered, an improvement in retrieving the partitioning of soluble species and especially nitrate is observed. A higher production in sulfate could help interpret the discrepancy of global model calculations with observed sulfate concentrations in Europe in wintertime

Coupling quasi-spectral microphysics with multiphase chemistry: a case study of a polluted air mass at the top of the Puy de Dôme mountain (France)

International audienc

Role of sublimation and riming in the precipitation distribution in the Kananaskis Valley, Alberta, Canada

International audienceThe phase of precipitation and its distribution at the surface can affect water resources and the regional water cycle of a region. A field project was held in March-April 2015 on the eastern slope of the Canadian Rockies to document precipitation characteristics and associated atmospheric conditions. During the project, 60 % of the particles documented were rimed in relatively warm and dry conditions. Rain-snow transitions also occurred aloft and at the surface in sub-saturated conditions. Ice-phase precipitation falling through a saturated atmospheric layer with temperatures > 0 • C will start melting. In contrast, if the melting layer is sub-saturated, the ice-phase precipitation undergoes sublimation, which increases the depth of the rain-snow transition. In this context, this study investigates the role of sub-limation and riming in precipitation intensity and type reaching the surface in the Kananaskis Valley, Alberta, during March-April 2015. To address this, a set of numerical simulations of an event of mixed precipitation observed at the surface was conducted. This event on 31 March 2015 was documented with a set of devices at the main observation site (Kananaskis Emergency Services, KES), including a precipitation gauge, disdrometer, and micro rain radar. Sensitivity experiments were performed to assess the impacts of temperature changes from sublimation and the role of the production of graupel (riming) aloft in the surface precipitation evolution. A warmer environment associated with no temperature changes from sublimation leads to a peak in the intensity of graupel at the surface. When the formation of grau-pel is not considered, the maximum snowfall rate occurred at later times. Results suggest that unrimed snow reaching the surface is formed on the western flank and is advected eastward. In contrast, graupel would form aloft in the Kananaskis Valley. The cooling from sublimation and melting by rimed particles increases the vertical shear near KES. Overall, this study illustrated that the presence of graupel influenced the surface evolution of precipitation type in the valley due to the horizontal transport of precipitation particles

Impact of radical versus non-radical pathway in the Fenton chemistry on the iron redox cycle in clouds

International audienc

Développement d'un nouveau schéma de physique des nuages dans le modèle de méso-échelle MésoNH pour l'étude des interactions aérosol-nuage

TOULOUSE3-BU Sciences (315552104) / SudocTOULOUSE-Observ. Midi Pyréné (315552299) / SudocSudocFranceF