Organic nitrate aerosol formation via NO&amp;lt;sub&amp;gt;3&amp;lt;/sub&amp;gt; + biogenic volatile organic compounds in the southeastern United States

Ayres, B. R.; Allen, Hannah M.; Draper, Danielle C.; Brown, Steven S.; Wild, R. J.; Jimenez, José L.; Day, Douglas A.; Campuzano‐Jost, Pedro; Hu, Weiwei; Gouw, J. A. de; Koss, A.; Cohen, R. C.; Duffey, K.; Romer, P.; Baumann, Karsten; Edgerton, Eric S.; Takahama, Satoshi; Thornton, Joel A.; Lee, B. H.; Lopez‐Hilfiker, Felipe D.; Mohr, Claudia; Wennberg, P. O.; Nguyen, Tran B.; Teng, Alex; Goldstein, Allen H.; Olson, K. F.; Fry, Juliane L.

doi:10.5194/acp-15-13377-2015

Cited by 145 publications

(212 citation statements)

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“…In areas with predominant monoterpene emissions, the background value is 3.1 ± 0.6 ‰ . Areas with a strong biomass burning and urban influence a background value of 1.7 ± 0.1 ‰ is reported, whereas ambient organic aerosol with a strong isoprene influence under low NO conditions shows an increased value of 6.5 ± 2.2 ‰ (Hu et al, 2015).…”

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“…Field measurements have shown that the major aerosol-phase product of monoterpene oxidation with nitrate radical is likely a hydroperoxy nitrate (C 10 H 17 NO 5 ) whereas the analogous isoprene oxidation product has a contribution of less than 1 % of the total organic nitrate and occurs more in gas phase (Ayres et al, 2015). Laboratory studies suggested that isoprene-derived 20 organic nitrates are formed from SOA reactions, but undergo substitution reactions in which nitrate is substituted by sulfate (Darer et al, 2011).…”

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confidence: 99%

“…The extensive study by Hu et al (2015) 5 summarizes those with a focus on IEPOX-SOA measured by aerosol mass spectrometry. The tracer ion at mass to charge ratio (m/z) 82 (C 5 H 6 O) was identified to be related to IEPOX-SOA in combination with the ion at m/z 53 (C 4 H 5 ) (Robinson et al, 2011;Allan et al, 2014;Hu et al, 2015).…”

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“…The tracer ion at mass to charge ratio (m/z) 82 (C 5 H 6 O) was identified to be related to IEPOX-SOA in combination with the ion at m/z 53 (C 4 H 5 ) (Robinson et al, 2011;Allan et al, 2014;Hu et al, 2015). In order to quantify the amount of IEPOX-SOA measured by aerosol mass spectrometry, the ratio of the signal at m/z 82 to the whole organic signal was introduced and is defined as f 82 (e.g., Budisulistiorini et al, 2013;Allan et al, 2014;Hu et al, 2015). Background values of f 82 were calculated on the basis of different field studies 10 worldwide.…”

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“…Many studies reported on the difficulties to measure organic 10 nitrates quantitatively, but suggested also a possibility to estimate the amount or at least the presence of organic nitrates based on the measured ion ratios of NO + to NO + 2 using aerosol mass spectrometry (e.g., Bruns et al, 2010;Farmer et al, 2010;Rollins et al, 2010;Fry et al, 2013;Ayres et al, 2015;Kiendler-Scharr et al, 2016;Ng et al, 2017;Schneider et al, 2017).…”

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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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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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Ubiquity of organic nitrates from nighttime chemistry in the European submicron aerosol

Kiendler‐Scharr

Mensah

Friese

et al. 2016

Geophysical Research Letters

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216

225

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In the atmosphere nighttime removal of volatile organic compounds is initiated to a large extent by reaction with the nitrate radical (NO3) forming organic nitrates which partition between gas and particulate phase. Here we show based on particle phase measurements performed at a suburban site in the Netherlands that organic nitrates contribute substantially to particulate nitrate and organic mass. Comparisons with a chemistry transport model indicate that most of the measured particulate organic nitrates are formed by NO3 oxidation. Using aerosol composition data from three intensive observation periods at numerous measurement sites across Europe, we conclude that organic nitrates are a considerable fraction of fine particulate matter (PM1) at the continental scale. Organic nitrates represent 34% to 44% of measured submicron aerosol nitrate and are found at all urban and rural sites, implying a substantial potential of PM reduction by NOx emission control.

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Water Soluble Organic Nitrogen (WSON) in Ambient Fine Particles Over a Megacity in South China: Spatiotemporal Variations and Source Apportionment

Zhu

et al. 2017

JGR Atmospheres

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Organic nitrogen aerosols are complex mixtures and important compositions in ambient fine particulate matters (PM2.5), yet their sources and spatiotemporal patterns are not well understood particularly in regions influenced by intensive human activities. In this study, filter‐based ambient PM2.5 samples at four stations (one urban, two rural, plus one urban roadside) and PM samples from combustion sources (vehicle exhaust, ship emission, and biomass burning) were collected in the coastal megacity Guangzhou, south China, for determining water soluble organic nitrogen (WSON) along with other organic and inorganic species. The annual average WSON concentrations, as well as the ratios of WSON to water soluble total nitrogen, were all significantly higher at rural sites than urban sites. Average WSON concentrations at the four sites during the wet season were quite near each other, ranging from 0.41 to 0.49 μg/m3; however, they became 2 times higher at the rural sites than at the urban sites during the dry season. Five major sources for WSON were identified through positive matrix factorization analysis. Vehicle emission (29.3%), biomass burning (22.8%), and secondary formation (20.2%) were three dominant sources of WSON at the urban station, while vehicle emission (45.4%) and dust (28.6%) were two dominant sources at the urban roadside station. At the two rural sites biomass burning (51.1% and 34.1%, respectively) and secondary formation (17.8% and 30.5%, respectively) were dominant sources of WSON. Ship emission contributed 8–12% of WSON at the four sites. Natural vegetation seemed to have very minor contribution to WSON.

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Organic nitrate aerosol formation via NO<sub>3</sub> + biogenic volatile organic compounds in the southeastern United States

Cited by 145 publications

References 98 publications

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

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

Ubiquity of organic nitrates from nighttime chemistry in the European submicron aerosol

Water Soluble Organic Nitrogen (WSON) in Ambient Fine Particles Over a Megacity in South China: Spatiotemporal Variations and Source Apportionment

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