Contribution of isoprene-derived organosulfates to free tropospheric aerosol mass

Froyd, K. D.; Murphy, S. M.; Murphy, D. M.; Gouw, J. A. de; Eddingsaas, Nathan C.; Wennberg, P. O.

doi:10.1073/pnas.1012561107

Cited by 227 publications

(260 citation statements)

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“…The PALMS instrument observed that the isoprene-derived organosulfate, IEPOX sulfate ester, comprised <0.01% of submicron aerosol mass in Pasadena, which supports the negligible role of organosulfates in this location. (Note: The mass abundance for the IEPOX sulfate ester was determined using detailed laboratory calibrations that were performed for a previous study [Froyd et al, 2010].) Furthermore, FTIR measurements of organonitrates [Day et al, 2010] found that concentrations were less than 2% of the measured nitrate (by AMS) on average, which is much lower than the percentage estimated in Riverside (10%).…”

Section: Discussionmentioning

confidence: 99%

Organic aerosol composition and sources in Pasadena, California, during the 2010 CalNex campaign

et al. 2013

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Organic aerosols (OA) in Pasadena are characterized using multiple measurements from the California Research at the Nexus of Air Quality and Climate Change (CalNex) campaign. Five OA components are identified using positive matrix factorization including hydrocarbon‐like OA (HOA) and two types of oxygenated OA (OOA). The Pasadena OA elemental composition when plotted as H : C versus O : C follows a line less steep than that observed for Riverside, CA. The OOA components from both locations follow a common line, however, indicating similar secondary organic aerosol (SOA) oxidation chemistry at the two sites such as fragmentation reactions leading to acid formation. In addition to the similar evolution of elemental composition, the dependence of SOA concentration on photochemical age displays quantitatively the same trends across several North American urban sites. First, the OA/ΔCO values for Pasadena increase with photochemical age exhibiting a slope identical to or slightly higher than those for Mexico City and the northeastern United States. Second, the ratios of OOA to odd‐oxygen (a photochemical oxidation marker) for Pasadena, Mexico City, and Riverside are similar, suggesting a proportional relationship between SOA and odd‐oxygen formation rates. Weekly cycles of the OA components are examined as well. HOA exhibits lower concentrations on Sundays versus weekdays, and the decrease in HOA matches that predicted for primary vehicle emissions using fuel sales data, traffic counts, and vehicle emission ratios. OOA does not display a weekly cycle—after accounting for differences in photochemical aging —which suggests the dominance of gasoline emissions in SOA formation under the assumption that most urban SOA precursors are from motor vehicles.

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Section: Discussionmentioning

confidence: 99%

Organic aerosol composition and sources in Pasadena, California, during the 2010 CalNex campaign

et al. 2013

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“…From single particle mass spectrometric measurements IEPOX sulfate esters were identified in 80 % and 50 % of the analyzed particles measured at altitudes of 5 and 10 km in the tropical free troposphere, respectively (Froyd et al, 2010). In the boundary layer, IEPOX sulfate ester in aerosol particles did not occur.…”

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“…In the boundary layer, IEPOX sulfate ester in aerosol particles did not occur. This is explained by a low abundance of acidic aerosol particles acting as seed particles and with a relatively short time since the emission of isoprene (Froyd et al, 2010). However, with lofting of isoprene and its derivatives 35 above the boundary layer, it is suggested that IEPOX can partition more efficiently to acidic aerosol particles.…”

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Aircraft-based observations of isoprene epoxydiol-derived secondary organic aerosol (IEPOX-SOA) in the tropical upper troposphere over the Amazon region

Schulz¹,

Schneider²,

Holanda³

et al. 2018

Preprint

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Abstract. During the ACRIDICON-CHUVA field project (September -October 2014; based in Manaus, Brazil) aircraftbased in-situ measurements of aerosol chemical composition were conducted in the tropical troposphere over the Amazon using the High Altitude and Long Range Research Aircraft (HALO), covering altitudes from the boundary layer height up to 14.4 km. The submicron non-refractory aerosol was characterized by flash-vaporization/electron impact-ionization aerosol particle mass spectrometry. The results show that significant secondary organic aerosol (SOA) formation by isoprene oxidation 5 products occurs in the upper troposphere, leading to increased organic aerosol mass concentrations above 10 km altitude.The median organic mass concentrations in the upper troposphere above 10 km range between 1.0 and 2.1 µg m −3 (referring to standard temperature and pressure; STP) with interquartile ranges of 0.6 to 3.0 µg m −3 (STP), representing 70 % of the total submicron non-refractory aerosol particle mass. The presence of isoprene epoxydiol-derived isoprene secondary organic aerosol (IEPOX-SOA) was confirmed by marker peaks in the mass spectra. We estimate the contribution of IEPOX-SOA to the 10 total organic aerosol in the upper troposphere to be about 20 %. After isoprene emission from vegetation, oxidation processes 1 Atmos. Chem. Phys. Discuss., https://doi.org/10.5194/acp-2018-232 Manuscript under review for journal Atmos. Chem. Phys. Discussion started: 9 April 2018 c Author(s) 2018. CC BY 4.0 License. occur at low altitudes and/or during transport to higher altitudes, which may lead to the formation of IEPOX (one oxidation product of isoprene). Reactive uptake or condensation of IEPOX on pre-existing particles leads to IEPOX-SOA formation and subsequently increasing organic mass in the upper troposphere. This organic mass increase was accompanied by an increase of the nitrate mass concentrations, most likely due to NO x production by lightning. We further found that the ammonium contained in the aerosol particles is not sufficient to neutralize the particulate sulfate and nitrate. Analysis of the ion ratio of 5 NO + to NO + 2 indicated that nitrate in the upper troposphere exists mainly in the form of organic nitrate. IEPOX-SOA and organic nitrates are coincident with each other, indicating that IEPOX-SOA forms in the upper troposphere either on acidic nitrate particles forming organic nitrates derived from IEPOX or on already neutralized organic nitrate aerosol particles.

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“…SOA has been implicated in cardiovascular disease (Pope III and Dockery, 2006) and as an important driver of climate change (Hallquist et al, 2009). 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.…”

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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Contribution of isoprene-derived organosulfates to free tropospheric aerosol mass

Cited by 227 publications

References 42 publications

Organic aerosol composition and sources in Pasadena, California, during the 2010 CalNex campaign

Organic aerosol composition and sources in Pasadena, California, during the 2010 CalNex campaign

Aircraft-based observations of isoprene epoxydiol-derived secondary organic aerosol (IEPOX-SOA) in the tropical upper troposphere over the Amazon region

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

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