Secondary organic aerosol formation from isoprene photooxidation during  cloud condensation–evaporation cycles

Bregonzio-Rozier, L.; Giorio, Chiara; Siekmann, F.; Pangui, Edouard; Morales, Sébastien B.; Temime-Roussel, Brice; Gratien, Aline; Michoud, Vincent; Cazaunau, Mathieu; DeWitt, H. Langley; Tapparo, Andrea; Monod, Anne; Doussin, Jean‐François

doi:10.5194/acp-16-1747-2016

Cited by 29 publications

(44 citation statements)

References 79 publications

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“…However, actual cloud‐induced SOA formation in droplets is more complex. Isoprene/NO x photooxidation during cloud condensation‐evaporation cycles was observed to form metastable SOA composed of organics, nitrate, and ammonium fragments [ Brégonzio‐Rozier et al ., ]. Quantitative assessments of SOA yields formed in clouds, and model predictions, warrant further study and require careful assessments of gas phase/chamber wall repartitioning after cloud dissipation.…”

Section: Soa Interaction With Cloudsmentioning

confidence: 99%

Recent advances in understanding secondary organic aerosol: Implications for global climate forcing

Shrivastava

Cappa

Fan

et al. 2017

Reviews of Geophysics

723

668

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Anthropogenic emissions and land use changes have modified atmospheric aerosol concentrations and size distributions over time. Understanding preindustrial conditions and changes in organic aerosol due to anthropogenic activities is important because these features (1) influence estimates of aerosol radiative forcing and (2) can confound estimates of the historical response of climate to increases in greenhouse gases. Secondary organic aerosol (SOA), formed in the atmosphere by oxidation of organic gases, represents a major fraction of global submicron‐sized atmospheric organic aerosol. Over the past decade, significant advances in understanding SOA properties and formation mechanisms have occurred through measurements, yet current climate models typically do not comprehensively include all important processes. This review summarizes some of the important developments during the past decade in understanding SOA formation. We highlight the importance of some processes that influence the growth of SOA particles to sizes relevant for clouds and radiative forcing, including formation of extremely low volatility organics in the gas phase, acid‐catalyzed multiphase chemistry of isoprene epoxydiols, particle‐phase oligomerization, and physical properties such as volatility and viscosity. Several SOA processes highlighted in this review are complex and interdependent and have nonlinear effects on the properties, formation, and evolution of SOA. Current global models neglect this complexity and nonlinearity and thus are less likely to accurately predict the climate forcing of SOA and project future climate sensitivity to greenhouse gases. Efforts are also needed to rank the most influential processes and nonlinear process‐related interactions, so that these processes can be accurately represented in atmospheric chemistry‐climate models.

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Section: Soa Interaction With Cloudsmentioning

confidence: 99%

Recent advances in understanding secondary organic aerosol: Implications for global climate forcing

Shrivastava

Cappa

Fan

et al. 2017

Reviews of Geophysics

723

668

View full text Add to dashboard Cite

show abstract

“…The kinetics database is based on existing recommendations and compilations (Buxton et al, 1988;Ross et al, 1998;Herrmann, 2003;Herrmann et al, 2010) with additional data collected from recent literature. In exceptional cases, where no other data existed, data from unpublished TROPOS measurements have been used for the database as well.…”

Section: Evaluation Of Experimental Kinetic Datamentioning

confidence: 99%

Development of a protocol for the auto-generation of explicit aqueous-phase oxidation schemes of organic compounds

et al. 2019

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Abstract. This paper presents a new CAPRAM–GECKO-A protocol for mechanism auto-generation of aqueous-phase organic processes. For the development, kinetic data in the literature were reviewed and a database with 464 aqueous-phase reactions of the hydroxyl radical with organic compounds and 130 nitrate radical reactions with organic compounds has been compiled and evaluated. Five different methods to predict aqueous-phase rate constants have been evaluated with the help of the kinetics database: gas–aqueous phase correlations, homologous series of various compound classes, radical reactivity comparisons, Evans–Polanyi-type correlations, and structure–activity relationships (SARs). The quality of these prediction methods was tested as well as their suitability for automated mechanism construction. Based on this evaluation, SARs form the basis of the new CAPRAM–GECKO-A protocol. Evans–Polanyi-type correlations have been advanced to consider all available H atoms in a molecule besides the H atoms with only the weakest bond dissociation enthalpies (BDEs). The improved Evans–Polanyi-type correlations are used to predict rate constants for aqueous-phase NO3 and organic compounds reactions. Extensive tests have been performed on essential parameters and on highly uncertain parameters with limited experimental data. These sensitivity studies led to further improvements in the new CAPRAM–GECKO-A protocol but also showed current limitations. Biggest uncertainties were observed in uptake processes and the estimation of Henry's law coefficients as well as radical chemistry, in particular the degradation of alkoxy radicals. Previous estimation methods showed several deficits, which impacted particle growth. For further evaluation, a 1,3,5-trimethylbenzene oxidation experiment has been performed in the aerosol chamber “Leipziger Aerosolkammer” (LEAK) at high relative humidity conditions and compared to a multiphase mechanism using the Master Chemical Mechanism (MCMv3.2) in the gas phase and using a methylglyoxal oxidation scheme of about 600 reactions generated with the new CAPRAM–GECKO-A protocol in the aqueous phase. While it was difficult to evaluate single particle constituents due to concentrations close to the detection limits of the instruments applied, the model studies showed the importance of aqueous-phase chemistry in respect to secondary organic aerosol (SOA) formation and particle growth. The new protocol forms the basis for further CAPRAM mechanism development towards a new version 4.0. Moreover, it can be used as a supplementary tool for aerosol chambers to design and analyse experiments of chemical complexity and help to understand them on a molecular level.

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“…The presence of acids as main contributors to the aqueous phase organic composition shows the potential for cloud reactivity to be a source of acids (Chameides, 1984). The total amount of organic acids (including formic and acetic acids) in both phases is almost doubled in less than 1 h by the aqueous phase sources, from approximately 0.48 ppbv of gaseous organic acids before the cloud to a total of 0.98 ppbv of organic acids in both phases (see Supplement SM7).…”

Section: Gas Chemical Reactivitymentioning

confidence: 99%

CLEPS 1.0: A new protocol for cloud aqueous phase oxidation of VOC mechanisms

et al. 2017

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A new detailed aqueous phase mechanism named the Cloud Explicit Physico-chemical Scheme (CLEPS 1.0) is proposed to describe the oxidation of water soluble organic compounds resulting from isoprene oxidation. It is based on structure activity relationships (SARs) which provide global rate constants together with branching ratios for HO · abstraction and addition on atmospheric organic compounds. The GROMHE SAR allows the evaluation of Henry's law constants for undocumented organic compounds. This new aqueous phase mechanism is coupled with the MCM v3.3.1 gas phase mechanism through a mass transfer scheme between gas phase and aqueous phase. The resulting multiphase mechanism has then been implemented in a model based on the Dynamically Simple Model for Atmospheric Chemical Complexity (DSMACC) using the Kinetic PreProcessor (KPP) that can serve to analyze data from cloud chamber experiments and field campaigns.The simulation of permanent cloud under low-NO x conditions describes the formation of oxidized monoacids and diacids in the aqueous phase as well as a significant influence on the gas phase chemistry and composition and shows that the aqueous phase reactivity leads to an efficient fragmentation and functionalization of organic compounds.

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Secondary organic aerosol formation from isoprene photooxidation during cloud condensation–evaporation cycles

Cited by 29 publications

References 79 publications

Recent advances in understanding secondary organic aerosol: Implications for global climate forcing

Recent advances in understanding secondary organic aerosol: Implications for global climate forcing

Development of a protocol for the auto-generation of explicit aqueous-phase oxidation schemes of organic compounds

CLEPS 1.0: A new protocol for cloud aqueous phase oxidation of VOC mechanisms

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