Kinetics of OH-initiated oxidation of oxygenated organic compounds in the aqueous phase: new rate constants, structure–activity relationships and atmospheric implications

Monod, Anne; Poulain, Laurent; Grubert, S.; Voisin, Didier; Wortham, Henri

doi:10.1016/j.atmosenv.2005.03.019

Cited by 104 publications

(127 citation statements)

References 48 publications

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“…Volatile organic compounds in the atmosphere oxidize with the products of this chemistry, contributing to the formation of secondary organic aerosols (SOAs) (3,4). Current model predictions, however, do not agree with findings of field measurements and highlight the importance of understanding organic reaction mechanisms, which are expected to affect the oxidizing capacity of the atmosphere, the formation of SOAs, and climate-relevant aerosol properties (1)(2)(3)(4)(5)(6)(7)(8)(9)(10). Organic polymers have been identified as important contributors to SOAs.…”

mentioning

confidence: 82%

Photochemistry of aqueous pyruvic acid

Griffith

Carpenter

Shoemaker³

et al. 2013

Proc. Natl. Acad. Sci. U.S.A.

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The study of organic chemistry in atmospheric aerosols and cloud formation is of interest in predictions of air quality and climate change. It is now known that aqueous phase chemistry is important in the formation of secondary organic aerosols. Here, the photoreactivity of pyruvic acid (PA; CH 3 COCOOH) is investigated in aqueous environments characteristic of atmospheric aerosols. PA is currently used as a proxy for α-dicarbonyls in atmospheric models and is abundant in both the gas phase and the aqueous phase (atmospheric aerosols, fog, and clouds) in the atmosphere. The photoreactivity of PA in these phases, however, is very different, thus prompting the need for a mechanistic understanding of its reactivity in different environments. Although the decarboxylation of aqueous phase PA through UV excitation has been studied for many years, its mechanism and products remain controversial. In this work, photolysis of aqueous PA is shown to produce acetoin (CH 3 CHOHCOCH 3 ), lactic acid (CH 3 CHOHCOOH), acetic acid (CH 3 COOH), and oligomers, illustrating the progression from a three-carbon molecule to four-carbon and even six-carbon molecules through direct photolysis. These products are detected using vibrational and electronic spectroscopy, NMR, and MS, and a reaction mechanism is presented accounting for all products detected. The relevance of sunlight-initiated PA chemistry in aqueous environments is then discussed in the context of processes occurring on atmospheric aerosols.

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mentioning

confidence: 82%

Photochemistry of aqueous pyruvic acid

Griffith

Carpenter

Shoemaker³

et al. 2013

Proc. Natl. Acad. Sci. U.S.A.

126

289

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“…The aqueous phase oxidation of organic compounds has mainly been investigated at 298 K, which is not relevant to the temperatures encountered in cloud/fog waters, and only a limited number of studies have explored the temperature dependence of the rate constants for reaction of OH with organic compounds at low ionic strength, representative of cloud/fog droplets (Chin and Wine, 1994;Buxton et al, 1997;Ervens et al, 2003b;Gligorovski and Herrmann, 2004;Poulain et al, 2007;Gligorovski et al, 2009). Based on these studies, structure activity relationships have been proposed to predict rate constants for the reaction of OH radicals with organic compounds at 298 K (Gligorovski and Herrmann, 2004;Monod et al, 2005;Monod and Doussin, 2008;Morozov et al, 2008;Gligorovski et al, 2009). Nevertheless, many aqueous phase oxidation reactions have yet to be investigated, especially for non-aliphatic compounds, and therefore are not considered in current models.…”

Section: Aqueous Phase Oxidation Of Organic Compoundsmentioning

confidence: 99%

The formation, properties and impact of secondary organic aerosol: current and emerging issues

et al. 2009

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Abstract. Secondary organic aerosol (SOA) accounts for a significant fraction of ambient tropospheric aerosol and a detailed knowledge of the formation, properties and transformation of SOA is therefore required to evaluate its impact on atmospheric processes, climate and human health. The chemical and physical processes associated with SOA formation are complex and varied, and, despite considerable progress in recent years, a quantitative and predictive understanding of SOA formation does not exist and therefore represents a major research challenge in atmospheric science. This review begins with an update on the current state of knowledge on the global SOA budget and is followed by an overview of the atmospheric degradation mechanisms for SOA precursors, gas-particle partitioning theory and the analytical techniques used to determine the chemical composition of SOA. A survey of recent laboratory, field and modeling studies is also presented. The following topical and emerging issues are highlighted and discussed in detail: molecular characterization of biogenic SOA constituents, condensed phase reactions and oligomerization, the interaction of atmospheric organic components with sulfuric acid, the chemical and photochemical processing of organics in the atmospheric aqueous phase, aerosol formation from real plant emissions, interaction of atmospheric organic components with water, thermodynamics and mixtures in atmospheric models. Finally, the major challenges ahead in laboratory, field and modeling studies of SOA are discussed and recommendations for future research directions are proposed.

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“…If aromatic and aliphatic carbon form the basis of the BC structure, the hydroxyl carbons in KB may correspond to the structure of "vitrinite" or K. The presence of this structure is rational because "vitrinite" or K in the dust comprises oxidation products formed by inter-molecular combination process. Multi-hydroxyl and ether functional groups are characteristic of oxidation products from VOCs (Monod et al, 2005). Recently, many low molecular weight multi-hydroxyl and ether compounds were identified in total suspended particles Bi et al, 2008).…”

Section: Solid State Cp/mas 13 C Nmr Spectroscopymentioning

confidence: 99%