Evidence for Organosulfates in Secondary Organic Aerosol

Surratt, Jason D.; Kroll, J. H.; Kleindienst, Tadeusz E.; Edney, Edward O.; Claeys, Magda; Sorooshian, Armin; Ng, N. L.; Offenberg, John H.; Lewandowski, Michael; Jaoui, Mohammed; Flagan, Richard C.; Seinfeld, John H.

doi:10.1021/es062081q

Cited by 633 publications

(946 citation statements)

References 44 publications

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“…O rganonitrates (ON, i.e., RONO 2 ) and organosulfates (OS, i.e., ROSO 3 H) are known to be present in secondary organic aerosol (SOA) (1)(2)(3)(4), and are a nearly unexplored but potentially important aspect of atmospheric chemistry. The mechanisms behind ON and OS production and aging are poorly understood and generally ignored in models due in part to a lack of measurement approaches.…”

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confidence: 99%

“…OS (i.e., ROSO 3 H) have been observed in both laboratorygenerated and ambient organic aerosol (OA) using negative ion (−) electrospray ionization (ESI)-MS techniques, resulting in the understanding that OS form in ambient aerosol from the oxidation of biogenic VOC in the presence of acidified sulfate aerosol (4,20). Although their prevalence in ambient aerosol remains unclear, further evidence for substantial OS contributions to SOA come from rainwater studies (21).…”

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“…OS fractions of this order would cause an error in the evaluation of acidity using nominally inorganic ions (24) and constitute a fraction of OA that is not accounted for in current models. Further, while chamber studies have focused on OS formation from the uptake of biogenic VOC oxidation products on acidified sulfate aerosol (4,20,23), anthropogenic VOC oxidation products likely also form OS.…”

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Response of an aerosol mass spectrometer to organonitrates and organosulfates and implications for atmospheric chemistry

Farmer

Matsunaga

Docherty

et al. 2010

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

523

562

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Organonitrates (ON) are important products of gas-phase oxidation of volatile organic compounds in the troposphere; some models predict, and laboratory studies show, the formation of large, multifunctional ON with vapor pressures low enough to partition to the particle phase. Organosulfates (OS) have also been recently detected in secondary organic aerosol. Despite their potential importance, ON and OS remain a nearly unexplored aspect of atmospheric chemistry because few studies have quantified particulate ON or OS in ambient air. We report the response of a high-resolution time-of-flight aerosol mass spectrometer (AMS) to aerosol ON and OS standards and mixtures. We quantify the potentially substantial underestimation of organic aerosol O/C, commonly used as a metric for aging, and N/C. Most of the ONnitrogen appears as NO þ x ions in the AMS, which are typically dominated by inorganic nitrate. Minor organonitrogen ions are observed although their identity and intensity vary between standards. We evaluate the potential for using NO þ x fragment ratios, organonitrogen ions, HNO þ 3 ions, the ammonium balance of the nominally inorganic ions, and comparison to ion-chromatography instruments to constrain the concentrations of ON for ambient datasets, and apply these techniques to a field study in Riverside, CA. OS manifests as separate organic and sulfate components in the AMS with minimal organosulfur fragments and little difference in fragmentation from inorganic sulfate. The low thermal stability of ON and OS likely causes similar detection difficulties for other aerosol mass spectrometers using vaporization and/or ionization techniques with similar or larger energy, which has likely led to an underappreciation of these species.atmospheric chemistry | organic aerosol | organic nitrate | organic sulfate | SOA O rganonitrates (ON, i.e., RONO 2 ) and organosulfates (OS, i.e., ROSO 3 H) are known to be present in secondary organic aerosol (SOA) (1-4), and are a nearly unexplored but potentially important aspect of atmospheric chemistry. The mechanisms behind ON and OS production and aging are poorly understood and generally ignored in models due in part to a lack of measurement approaches. ON have recently been identified as significant components (15-35%) of NO y in the gas-phase (5, 6) and serve as indicators of ozone production (7). Oceans and certain industrial processes directly emit ON, but these are generally short-chain alkyl nitrates that exist only in the gas-phase and constitute a minor fraction of atmospheric ON (6,8). Most atmospheric ON are produced either by photochemical (OH-initiated) or nocturnal (NO 3 -initiated) oxidation reactions of anthropogenic and biogenic volatile organic compounds (VOCs). These reactions can produce large, multifunctional ON with vapor pressures potentially low enough to condense and form SOA. During photochemical oxidation of VOCs in the presence of nitrogen oxides, ON are minor products of peroxy radical ðRO 2 Þ þ NO reactions. These reactions produce ON with yields of ...

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Response of an aerosol mass spectrometer to organonitrates and organosulfates and implications for atmospheric chemistry

Farmer

Matsunaga

Docherty

et al. 2010

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

523

562

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“…The existence of aerosol as seed particles seems to be necessary (Surratt et al, 2010;Lin et al, 2012), but also the 25 acidity of aerosol can influence the formation yield of IEPOX-SOA. Laboratory and field studies found a correlation between IEPOX-SOA and sulfate, which is related to the acidity of aerosol (Surratt et al, 2007;Budisulistiorini et al, 2013). Although the IEPOX pathway is considered as the dominant one, further laboratory studies show that also other gas-phase reactions of ISOPOOH with multifunctional hydroperoxides contribute to the formation of isoprene-derived SOA (e.g., Krechmer et al, 2015;Liu et al, 2016b;Riva et al, 2016).…”

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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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“…to particle acidity, which enhances isoprene SOA formation through acid-catalyzed reactive uptake and multiphase chemistry of IEPOX and MAE (Surratt et al, 2007Gaston et al, 2014;Riedel et al, 2015), while NO x determines whether the oxidation pathway leading to IEPOX or MAE/HMML predominates (Lin et al, 2013b;. Isoprene SOA comprises a large portion of global atmospheric fine particles (PM 2.5 , aerosol with aerodynamic diameters ≤ 2.5 µm) (Carlton et al, 2009;Henze et al, 2008), but few studies have focused on its health implications .…”

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In vitro exposure to isoprene-derived secondary organic aerosol by direct deposition and its effects on <i>COX-2</i> and <i>IL-8</i> gene expression

et al. 2016

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Abstract. Atmospheric oxidation of isoprene, the most abundant non-methane hydrocarbon emitted into Earth's atmosphere primarily from terrestrial vegetation, is now recognized as a major contributor to the global secondary organic aerosol (SOA) burden. Anthropogenic pollutants significantly enhance isoprene SOA formation through acidcatalyzed heterogeneous chemistry of epoxide products. Since isoprene SOA formation as a source of fine aerosol is a relatively recent discovery, research is lacking on evaluating its potential adverse effects on human health. The objective of this study was to examine the effect of isoprenederived SOA on inflammation-associated gene expression in human lung cells using a direct deposition exposure method. We assessed altered expression of inflammationrelated genes in human bronchial epithelial cells (BEAS-2B) exposed to isoprene-derived SOA generated in an outdoor chamber facility. Measurements of gene expression of known inflammatory biomarkers interleukin 8 (IL-8) and cyclooxygenase 2 (COX-2) in exposed cells, together with complementary chemical measurements, showed that a dose of 0.067 µg cm −2 of SOA from isoprene photooxidation leads to statistically significant increases in IL-8 and COX-2 mRNA levels. Resuspension exposures using aerosol filter extracts corroborated these findings, supporting the conclusion that isoprene-derived SOA constituents induce the observed changes in mRNA levels. The present study is an attempt to examine the early biological responses of isoprene SOA exposure in human lung cells.

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Evidence for Organosulfates in Secondary Organic Aerosol

Cited by 633 publications

References 44 publications

Response of an aerosol mass spectrometer to organonitrates and organosulfates and implications for atmospheric chemistry

Response of an aerosol mass spectrometer to organonitrates and organosulfates and implications for atmospheric chemistry

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

In vitro exposure to isoprene-derived secondary organic aerosol by direct deposition and its effects on <i>COX-2</i> and <i>IL-8</i> gene expression

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Evidence for Organosulfates in Secondary Organic Aerosol

Cited by 633 publications

References 44 publications

Response of an aerosol mass spectrometer to organonitrates and organosulfates and implications for atmospheric chemistry

Response of an aerosol mass spectrometer to organonitrates and organosulfates and implications for atmospheric chemistry

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

In vitro exposure to isoprene-derived secondary organic aerosol by direct deposition and its effects on &lt;i&gt;COX-2&lt;/i&gt; and &lt;i&gt;IL-8&lt;/i&gt; gene expression

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In vitro exposure to isoprene-derived secondary organic aerosol by direct deposition and its effects on <i>COX-2</i> and <i>IL-8</i> gene expression