Oligomer and SOA formation through aqueous phase photooxidation of methacrolein and methyl vinyl ketone

Liu, Yao; Siekmann, F.; Renard, P.; Zein, Atallah El; Salque, G.; Haddad, Imad El; Temime-Roussel, Brice; Voisin, Didier; Thissen, R.; Monod, Anne

doi:10.1016/j.atmosenv.2011.12.012

Cited by 66 publications

(89 citation statements)

References 32 publications

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“…SOA in the atmosphere, especially in the presence of water (Loeffler et al 2006;Altieri et al, 2006;Carlton et al, 2007;Volkamer et al, 2009;Perri et al, 2009;Ervens and Volkamer, 2010;Tan et al, 2010;Lee et al, 2012;Ervens et al, 2011;Liu et al, 2012;Ortiz-Montalvo et al 2012). The oligomeric condensation processes of carbonyl compounds in the atmosphere are only partially understood, and a large effort currently concentrates on the determination of the oligomerization mechanisms.…”

Section: Published By Copernicus Publications On Behalf Of the Europementioning

confidence: 99%

Structure–activity relationship for the estimation of OH-oxidation rate constants of carbonyl compounds in the aqueous phase

2013

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Abstract. In the atmosphere, one important class of reactions occurs in the aqueous phase in which organic compounds are known to undergo oxidation towards a number of radicals, among which OH radicals are the most reactive oxidants. In 2008, Monod and Doussin have proposed a new structure-activity relationship (SAR) to calculate OHoxidation rate constants in the aqueous phase. This estimation method is based on the group-additivity principle and was until now limited to alkanes, alcohols, acids, bases and related polyfunctional compounds. In this work, the initial SAR is extended to carbonyl compounds, including aldehydes, ketones, dicarbonyls, hydroxy carbonyls, acidic carbonyls, their conjugated bases, and the hydrated form of all these compounds. To do so, only five descriptors have been added and none of the previously attributed descriptors were modified. This extension leads now to a SAR which is based on a database of 102 distinct compounds for which 252 experimental kinetic rate constants have been gathered and reviewed. The efficiency of this updated SAR is such that 58 % of the rate constants could be calculated within ± 20 % of the experimental data and 76 % within ± 40 % (respectively 41 and 72 % for the carbonyl compounds alone).

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Section: Published By Copernicus Publications On Behalf Of the Europementioning

confidence: 99%

Structure–activity relationship for the estimation of OH-oxidation rate constants of carbonyl compounds in the aqueous phase

2013

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“…First of all, the fate of isoprene in the condensed phase shall be examined, as isoprene has been recognized as a major SOA precursor through its first generation products methacrolein (MACR) and methyl vinyl ketone (MVK) (Pandis et al, 1991;Carlton et al, 2009), which were found to be important oligomer precursors in the condensed phase (El Haddad et al, 2009;Liu et al, 2012b;Renard et al, 2013). On this specific point, the study of Renard et al (2015), based on the photo-oxidation of MVK into a photo-reactor, revealed that considering only a first-order rate constant to represent the formation of oligomers is not appropriate, as the oxidation of MVK by OH was (in the condensed phase of the deliquescent aerosol) governed by a kinetic competition between functionalization and oligomerization, which depends on the precursor initial concentration.…”

Section: Oligomer Formation From Isoprenementioning

confidence: 99%

“…Several observations and experiments reported in the literature point to the irreversibility -at least partial -of the oligomerization process. According to a recent study of Liu et al (2012b), the formation of oligomers from methacrolein and methyl vinyl ketone (isoprene oxidation products) is irreversible. This assumption is supported by the recent works of Hall and Johnston (2012a), who investigated the thermal stability of a SOA matrix including 50 % of oligomeric species formed by the ozonolysis of α-pinene: the authors concluded that, at ambient temperatures, oligomeric species should be non-volatile by structure.…”

Section: Further Developments For Oligomer Formation Dynamicsmentioning

confidence: 99%

Oligomer formation in the troposphere: from experimental knowledge to 3-D modeling

et al. 2016

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Abstract. The organic fraction of atmospheric aerosols has proven to be a critical element of air quality and climate issues. However, its composition and the aging processes it undergoes remain insufficiently understood. This work builds on laboratory knowledge to simulate the formation of oligomers from biogenic secondary organic aerosol (BSOA) in the troposphere at the continental scale. We compare the results of two different modeling approaches, a first-order kinetic process and a pH-dependent parameterization, both implemented in the CHIMERE air quality model (AQM) (www.lmd.polytechnique.fr/chimere), to simulate the spatial and temporal distribution of oligomerized secondary organic aerosol (SOA) over western Europe. We also included a comparison of organic carbon (OC) concentrations at two EMEP (European Monitoring and Evaluation Programme) stations. Our results show that there is a strong dependence of the results on the selected modeling approach: while the irreversible kinetic process leads to the oligomerization of about 50 % of the total BSOA mass, the pH-dependent approach shows a broader range of impacts, with a strong dependency on environmental parameters (pH and nature of aerosol) and the possibility for the process to be reversible. In parallel, we investigated the sensitivity of each modeling approach to the representation of SOA precursor solubility (Henry's law constant values). Finally, the pros and cons of each approach for the representation of SOA aging are discussed and recommendations are provided to improve current representations of oligomer formation in AQMs.

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“…Alternatively, there is evidence that radical processes may also contribute to the formation of oligomers in the aqueous phase. Kinetic studies of the formation of oligomers lead some authors to propose combination reactions of organic radicals during the aqueous phase direct photolysis of pyruvic acid (Guzmán et al 2006) (Figure 16) or during OH-initiated oxidation of methacrolein and methylvynilketone Liu et al 2010). For all aqueous phase studies, the formed oligomers have shown molecular masses up to 1400 Da (see the mass spectrum in Figure 15), and are thus non volatile material, which is likely a source of SOA after cloud's processing.…”

Section: Epj Web Of Conferencesmentioning

confidence: 99%

“…For all aqueous phase studies, the formed oligomers have shown molecular masses up to 1400 Da (see the mass spectrum in Figure 15), and are thus non volatile material, which is likely a source of SOA after cloud's processing. It has been shown very recently that oligomers, formed in the aqueous phase after photooxidation of methacrolein and methylvynilketone Zhang et al 2010), lead to the formation of significant amounts of organic aerosols after cloud's evaporation Liu et al 2010), and the obtained organic aerosol had specific hygroscopic and volatility properties ).…”

Section: Epj Web Of Conferencesmentioning

confidence: 99%

Aerosol formation and heterogeneous chemistry in the atmosphere

Monod

Liu

2011

EPJ Web of Conferences

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Abstract.A general presentation of the Earth's atmosphere is provided, with the associated photochemical processes and oxidizing capacity. The article focuses on the atmospheric reactivity of Volatile Organic Compounds (VOCs) and the associated reaction products in the gas phase (ozone, oxygenated organic compounds, organic nitrates . . . ) and in the particle phase, namely, the Secondary Organic Aerosols (SOA). The understanding of the processes leading to SOA formation is currently a "hot topic" because of: i) their high concentrations in the measured total organic matter, and ii) their potential important impacts on health and climate change. The initial theory of SOA formation was based on thermodynamic phase transfers of oxidized reaction products of VOCs, but it failed to explain the presence of high molecular weight (high-MW) compounds observed in SOA as well as a 1 to 2 orders of magnitude discrepancy between models and observations on the quantity of SOA. Therefore, different research investigations have been proposed such as heterogeneous and aqueous phase reactivity of organic compounds.

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Oligomer and SOA formation through aqueous phase photooxidation of methacrolein and methyl vinyl ketone

Cited by 66 publications

References 32 publications

Structure–activity relationship for the estimation of OH-oxidation rate constants of carbonyl compounds in the aqueous phase

Structure–activity relationship for the estimation of OH-oxidation rate constants of carbonyl compounds in the aqueous phase

Oligomer formation in the troposphere: from experimental knowledge to 3-D modeling

Aerosol formation and heterogeneous chemistry in the atmosphere

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