Radical‐initiated formation of organosulfates and surfactants in atmospheric aerosols

Nozière, Barbara; Ekström, Sanna; Alsberg, Tomas; Holmström, Sara

doi:10.1029/2009gl041683

Cited by 193 publications

(245 citation statements)

References 39 publications

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“…In the Amazon, Kourtchev et al (2016) previously found a similar subset of these unidentified CHOS compounds in SOA samples, suggesting a biogenic influence. Many organosulfates and nitrooxy-organosulfates, previously reported in laboratory studies, ambient aerosols, and cloud water as derived from monoterpene oxidation (Boone et al, 2015;Hamilton et al, 2013;Iinuma et al, 2007aIinuma et al, , b, 2009Kristensen et al, 2016;Kristensen and Glasius, 2011;Lin et al, 2012;Mazzoleni et al, 2012;Nguyen et al, 2012b;Nozière et al, 2010;O'Brien et al, 2014;Pratt et al, 2013;Stone et al, 2012;Surratt et al, 2008), were detected in the biogenic-influenced cloud water samples (Table 2), also consistent with monoterpene emissions along the air mass trajectories (Guenther et al, 2006). In this study, the required solid-phase extraction step precluded the detection of isoprene-derived organosulfates, which would have been removed prior to analysis.…”

Section: Biogenic Influencesupporting

confidence: 66%

“…Organosulfates are suggested to be formed from acidcatalyzed reactive uptake of epoxides onto sulfate aerosol (Surratt et al, 2010), as well as in-cloud radical-radical reactions involving sulfate radicals (Nozière et al, 2010;Perri et al, 2010;Schindelka et al, 2013). Isoprene-and monoterpene-derived organosulfates have been observed in cloud water over the southeastern US (Boone et al, 2015;Pratt et al, 2013).…”

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confidence: 99%

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Biogenic, urban, and wildfire influences on the molecular composition of dissolved organic compounds in cloud water

Cook¹,

Lin²,

Peng³

et al. 2017

Atmos. Chem. Phys.

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Abstract. Organic aerosol formation and transformation occurs within aqueous aerosol and cloud droplets, yet little is known about the composition of high molecular weight organic compounds in cloud water. Cloud water samples collected at Whiteface Mountain, New York, during AugustSeptember 2014 were analyzed by ultra-high-resolution mass spectrometry to investigate the molecular composition of dissolved organic carbon, with a focus on sulfur-and nitrogen-containing compounds. Organic molecular composition was evaluated in the context of cloud water inorganic ion concentrations, pH, and total organic carbon concentrations to gain insights into the sources and aqueous-phase processes of the observed high molecular weight organic compounds. Cloud water acidity was positively correlated with the average oxygen : carbon ratio of the organic constituents, suggesting the possibility for aqueous acid-catalyzed (prior to cloud droplet activation or during/after cloud droplet evaporation) and/or radical (within cloud droplets) oxidation processes. Many tracer compounds recently identified in laboratory studies of bulk aqueous-phase reactions were identified in the cloud water. Organosulfate compounds, with both biogenic and anthropogenic volatile organic compound precursors, were detected for cloud water samples influenced by air masses that had traveled over forested and populated areas. Oxidation products of long-chain (C 10−12 ) alkane precursors were detected during urban influence. Influence of Canadian wildfires resulted in increased numbers of identified sulfur-containing compounds and oligomeric species, including those formed through aqueous-phase reactions involving methylglyoxal. Light-absorbing aqueous-phase products of syringol and guaiacol oxidation were observed in the wildfire-influenced samples, and dinitroaromatic compounds were observed in all cloud water samples (wildfire, biogenic, and urban-influenced). Overall, the cloud water molecular composition depended on air mass source influence and reflected aqueous-phase reactions involving biogenic, urban, and biomass burning precursors.

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Section: Biogenic Influencesupporting

confidence: 66%

mentioning

confidence: 99%

Biogenic, urban, and wildfire influences on the molecular composition of dissolved organic compounds in cloud water

Cook¹,

Lin²,

Peng³

et al. 2017

Atmos. Chem. Phys.

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“…Seven different chemically distinct compounds based on the isoprene carbon backbone, containing epoxy, alcohol, nitrate, and/or sulfate functional groups, have now been identified in ambient SOA Claeys et al, 2004;Wang et al, 2005;Surratt et al, 2007;Altieri et al, 2009;Gómez-González et al, 2008;Surratt et al, 2008;Froyd et al, 2010). Some of these compounds are undoubtedly formed from gas phase processing (Perring et al, 2009a, b;Lockwood et al, 2010;Ng et al, 2008), of isoprene, while other compounds (such as organosulfates) clearly indicate that additional chemical processing is occurring on ambient SOA particles themselves (Cole-Filipiak et al, 2010;Paulot et al, 2009;Surratt et al, 2010;Chan et al, 2010;Minerath et al, 2008Eddingsaas et al, 2010;Szmigielski et al, 2010;Nozière et al, 2010;Rudzinski et al, 2009) We recently investigated some of the potential SOA-phase chemistry for isoprene-related compounds, and proposed an overall mechanism (shown in Fig. 1) that can rationalize the existence of five of the seven observed isoprene-derived SOA components (Darer et al, 2011).…”

Section: Introductionmentioning

confidence: 99%

Thermodynamics and kinetics of the hydrolysis of atmospherically relevant organonitrates and organosulfates

2011

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Abstract. The presence of alcohol, organonitrate, and organosulfate species related to the gaseous precursor isoprene in ambient secondary organic aerosol (SOA) has stimulated investigations of the nature of SOA-phase chemical processing. Recent work has suggested that certain isoprene-derived organonitrates are able to efficiently convert to organosulfates and alcohols on ambient SOA. In order to better understand the structure activity relationships previously observed for the isoprene-derived organonitrates and organosulfates, the hydrolysis reactions of a number of monofunctional and difunctional organonitrates and organosulfates with varying carbon substitution properties were investigated. Nuclear magnetic resonance techniques were used to study the bulk phase aqueous reactions of these organonitrates and organosulfates in order to determine hydrolysis reaction rate and, in some cases, thermodynamics information. Electronic structure calculations were also carried out to determine the enthalpy of hydrolysis for these species, and for the previously studied isoprene-derived species. The results suggest that while organonitrates and organosulfates are thermodynamically unstable with respect to the corresponding alcohols at standard state, only the tertiary organonitrates (and perhaps some tertiary organosulfates) are able to efficiently hydrolyze on SOA timescales and acidities.

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“…[32,33] Organic nitrogen and sulfur compounds have been observed to form in highly concentrated aqueous solutions relevant to wet aerosols. [6,[34][35][36][37] Evidence for the photochemical formation of organosulfates from GLY and other aldehydes is provided through studies of bulk sulfate solutions and through smog chamber experiments with ammonium sulfate seed particles and UV irradiation. [6,35,36] Aerosol mimic solutions containing GLY and inorganic ammonium salts have yielded products with carbon-nitrogen bonds in the absence of major atmospheric oxidants (i.e.…”

Section: Introductionmentioning

confidence: 99%

Glyoxal secondary organic aerosol chemistry: effects of dilute nitrate and ammonium and support for organic radical–radical oligomer formation

Kirkland¹,

Lim²,

Tan³

et al. 2013

Environ. Chem.

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Environmental context. Atmospheric waters (clouds, fogs and wet aerosols) are media in which gases can be converted into particulate matter. This work explores aqueous transformations of glyoxal, a water-soluble gas with anthropogenic and biogenic sources. Results provide new evidence in support of previously proposed chemical mechanisms. These mechanisms are beginning to be incorporated into transport models that link emissions to air pollution concentrations and behaviour.Abstract. Glyoxal (GLY) is ubiquitous in the atmosphere and an important aqueous secondary organic aerosol (SOA) precursor. At dilute (cloud-relevant) organic concentrations, OH radical oxidation of GLY has been shown to produce oxalate. GLY has also been used as a surrogate species to gain insight into radical and non-radical reactions in wet aerosols, where organic and inorganic concentrations are very high (in the molar region). The work herein demonstrates, for the first time, that tartarate forms from GLY þ OH . Tartarate is a key product in a previously proposed organic radical-radical reaction mechanism for oligomer formation from GLY oxidation. Previously published model predictions that include this GLY oxidation pathway suggest that oligomers are major products of OH radical oxidation at the high organic concentrations found in wet aerosols. The tartarate measurements herein provide support for this proposed oligomer formation mechanism. This paper also demonstrates, for the first time, that dilute (cloud or fog-relevant) concentrations of inorganic nitrogen (i.e. ammonium and nitrate) have little effect on the GLY þ OH chemistry leading to oxalate formation in clouds. This, and results from previous experiments conducted with acidic sulfate, increase confidence that the currently understood dilute GLY þ OH chemistry can be used to predict GLY SOA formation in clouds and fogs. It should be recognised that organic-inorganic interactions can play an important role in droplet evaporation chemistry and in wet aerosols. The chemistry leading to SOA formation in these environments is complex and remains poorly understood.

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Radical‐initiated formation of organosulfates and surfactants in atmospheric aerosols

Cited by 193 publications

References 39 publications

Biogenic, urban, and wildfire influences on the molecular composition of dissolved organic compounds in cloud water

Biogenic, urban, and wildfire influences on the molecular composition of dissolved organic compounds in cloud water

Thermodynamics and kinetics of the hydrolysis of atmospherically relevant organonitrates and organosulfates

Glyoxal secondary organic aerosol chemistry: effects of dilute nitrate and ammonium and support for organic radical–radical oligomer formation

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