Seasonal variations of fine particulate organosulfates derived from biogenic and anthropogenic hydrocarbons in the mid-Atlantic United States

L, Meade; Riva, Matthieu; Blomberg, Max Z.; Brock, Amanda K.; Qualters, Elisa Marie; Siejack, Richard A.; Kumar, Rajiv; Surratt, Jason D.; Kautzman, Kathryn E.

doi:10.1016/j.atmosenv.2016.09.028

Cited by 44 publications

(43 citation statements)

References 58 publications

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“…The average concentration of MAE/HMML‐derived OS (C 4 H 7 O 3 SO 4 − m/z 198.9918) in summer was about 32.2 times larger than that in winter (averagely 2.58 vs 0.08 ng m −3 ) (Table 1). Our observation was similar to those reported in the mid‐Atlantic region (1 ± 2 ng m −3 ) (Meade et al, 2016) and less than those from Denmark (4.5–7.1 ng m −3 ) (Nguyen et al, 2014) and Birmingham, Alabama (7.2–35.7 ng m −3 ) (Rattanavaraha et al, 2016).…”

Section: Resultssupporting

confidence: 92%

Molecular Characterization of Organosulfates in Highly Polluted Atmosphere Using Ultra‐High‐Resolution Mass Spectrometry

et al. 2020

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Organosulfates (OSs) have recently been observed to be a potentially important constituent of secondary organic aerosol (SOA); however, their molecular characterization in highly polluted atmospheres has not been probed in detail. This study thoroughly presents the characterization of OSs in polluted air and demonstrates their seasonal and diurnal variations, formation mechanisms, and contributions to organic aerosol. Atmospheric PM 2.5 samples were collected from an urban Shanghai site across the winter and summer of 2017. OSs were characterized by ultra-high-performance liquid chromatography (UHPLC) coupled with Orbitrap mass spectrometry (MS). Based on exact mass formulae in conjunction with previous chamber studies, hundreds of sulfur-containing compounds were tentatively identified as OSs. The number and abundance of OSs increased significantly during pollution episodes. The OSs in the clean aerosol samples were dominant in biogenic products, whereas the OSs in the polluted winter samples had distinctive anthropogenic characteristics. Aromatics and long-chain alkanes from anthropogenic emissions might be their precursors. By using synthesized standards, the total concentrations of 14 quantified OSs ranged 21.6-161 ng m −3 in summer and 5.85-84.3 ng m −3 in winter, respectively. Among these OSs, glycolic acid sulfate was the most abundant species (1.13-122 ng m −3 ). Further analysis of their seasonal and diurnal variations suggests possible contributions from multiple formation mechanisms, including acid-catalyzed and NO 3 -initiated oxidation reactions. Our results highlight that increased anthropogenic pollutant emissions (e.g., NO x and SO 2 ) can significantly enhance the SOA burden in biogenically influenced urban areas.

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Section: Resultssupporting

confidence: 92%

Molecular Characterization of Organosulfates in Highly Polluted Atmosphere Using Ultra‐High‐Resolution Mass Spectrometry

et al. 2020

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“…Among these SOA constituents, IEPOX-derived organosulfates (e.g., methyltetrol sulfates) have been widely detected in atmospheric aerosols and are estimated to account for 0.3 %-1.7 % of the total organic carbon (Chan et al, 2010;Froyd et al, 2010;Hatch et al, 2011;Lin et al, 2012;Stone et al, 2012;He et al, 2014;Budisulistiorini et al, 2015;Rattanavaraha et al, 2016;Meade et al, 2016;Hettiyadura et al, 2017). While the formation mechanisms of organosulfates have been extensively studied (Surratt et al, 2007(Surratt et al, , 2008Minerath et al, 2009;Cole-Filipiak et al, 2010;Nozière et al, 2010;Lin et al, 2012;Nguyen et al, 2014), their chemical transformations and stability remain unclear. These low-volatility organosulfates are preferentially present in particle phase and can be oxidized by gas-phase oxidants (e.g., OH radicals, ozone and nitrate radicals) at or near the aerosol surface throughout their atmospheric lifetimes.…”

Section: Introductionmentioning

confidence: 99%

Heterogeneous OH oxidation of isoprene-epoxydiol-derived organosulfates: kinetics, chemistry and formation of inorganic sulfate

et al. 2019

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Abstract. Acid-catalyzed multiphase chemistry of epoxydiols formed from isoprene oxidation yields the most abundant organosulfates (i.e., methyltetrol sulfates) detected in atmospheric fine aerosols in the boundary layer. This potentially determines the physicochemical properties of fine aerosols in isoprene-rich regions. However, chemical stability of these organosulfates remains unclear. As a result, we investigate the heterogeneous oxidation of aerosols consisting of potassium 3-methyltetrol sulfate ester (C5H11SO7K) by gas-phase hydroxyl (OH) radicals at a relative humidity (RH) of 70.8 %. Real-time molecular composition of the aerosols is obtained by using a Direct Analysis in Real Time (DART) ionization source coupled to a high-resolution mass spectrometer. Aerosol mass spectra reveal that 3-methyltetrol sulfate ester can be detected as its anionic form (C5H11SO7-) via direct ionization in the negative ionization mode. Kinetic measurements reveal that the effective heterogeneous OH rate constant is measured to be 4.74±0.2×10-13 cm3 molecule−1 s−1 with a chemical lifetime against OH oxidation of 16.2±0.3 days, assuming an OH radical concentration of 1.5×106 molecules cm−3. Comparison of this lifetime with those against other aerosol removal processes, such as dry and wet deposition, suggests that 3-methyltetrol sulfate ester is likely to be chemically stable over atmospheric timescales. Aerosol mass spectra only show an increase in the intensity of bisulfate ion (HSO4-) after oxidation, suggesting the importance of fragmentation processes. Overall, potassium 3-methyltetrol sulfate ester likely decomposes to form volatile fragmentation products and aqueous-phase sulfate radial anion (SO4⚫-). SO4⚫- subsequently undergoes intermolecular hydrogen abstraction to form HSO4-. These processes appear to explain the compositional evolution of 3-methyltetrol sulfate ester during heterogeneous OH oxidation.

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“…Among these SOA constituents, IEPOX-derived organosulfates (e.g. methyltetrol sulfates) have been widely detected in atmospheric aerosols and are estimated to account for 0.3-1.7 % of the total organic carbon (Chan et al, 15 2010;Froyd et al, 2010;Hatch et al, 2011;Lin et al, 2012;Stone et al, 2012;He et al, 2014;Budisulistiorini et al, 2015;Rattanavaraha et al, 2016;Meade et al, 2016;Hettiyadura et al 2017). While the formation mechanisms of organosulfates have been extensively studied (Surratt et al, 2007(Surratt et al, , 2008Minerath et al, 2009;Cole-Filipiak et al, 2010;Nozière et al, 2010;Lin et al, 2012;Nguyen et al, 2014), their chemical transformations and stability remain unclear.…”

Section: Introductionmentioning

confidence: 99%

Heterogeneous OH Oxidation of Isoprene Epoxydiol-Derived Organosulfates: Kinetics, Chemistry and Formation of Inorganic Sulfate

Lam¹,

Kwong²,

Poon³

et al. 2018

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Abstract. Acid-catalyzed multiphase chemistry of epoxydiols formed from isoprene oxidation yields the most abundant organosulfates (i.e., methyltetrol sulfates) detected in atmospheric fine aerosols. This potentially determines the physicochemical properties of fine aerosols in isoprene-rich regions. However, chemical stability of these organosulfates remains unclear. As a result, we investigate the heterogeneous oxidation of aerosols consisting of potassium 3-methyltetrol sulfate ester (C5H11SO7K) by gas-phase hydroxyl (OH) radicals through studying the oxidation kinetics and reaction products at a relative humidity (RH) of 70.8&#8201;%. Real-time molecular composition of the aerosols is obtained by using a Direct Analysis in Real Time (DART) ionization source coupled to a high-resolution mass spectrometer. Aerosol mass spectra reveal that 3-methyltetrol sulfate ester can be detected as its anionic form (C5H11SO7&#8722;) via direct ionization in the negative ionization mode. Kinetic measurements reveal that the effective heterogeneous OH rate constant is measured to be 4.74&#8201;&#177;&#8201;0.2&#8201;&#215;&#8201;10&#8722;13&#8201;cm3&#8201;molecule&#8722;1&#8201;s&#8722;1 with a chemical lifetime against OH oxidation of 16.2&#8201;&#177;&#8201;0.3&#8201;days. Comparison of this lifetime with those against other aerosol removal processes, such as dry and wet deposition, suggests that 3-methyltetrol sulfate ester is likely to be chemically stable over atmospheric timescales. Aerosol mass spectra only show an increase in the intensity of bisulfate ion (HSO4&#8722;) after oxidation, suggesting the absence of functionalization processes is likely attributable to the steric effect of substituted functional groups (e.g. methyl, alcohol and sulfate groups) on peroxy&#8211;peroxy radical reactions. Overall, potassium 3-methyltetrol sulfate ester likely decomposes to form volatile fragmentation products and aerosol-phase sulfate radial anion (SO4&#8226;&#8722;). SO4&#8226;&#8722; subsequently undergoes intermolecular hydrogen abstraction to form HSO4&#8722;. These processes appear to explain the compositional evolution of 3-methyltetrol sulfate ester during heterogeneous OH oxidation.

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Seasonal variations of fine particulate organosulfates derived from biogenic and anthropogenic hydrocarbons in the mid-Atlantic United States

Cited by 44 publications

References 58 publications

Molecular Characterization of Organosulfates in Highly Polluted Atmosphere Using Ultra‐High‐Resolution Mass Spectrometry

Molecular Characterization of Organosulfates in Highly Polluted Atmosphere Using Ultra‐High‐Resolution Mass Spectrometry

Heterogeneous OH oxidation of isoprene-epoxydiol-derived organosulfates: kinetics, chemistry and formation of inorganic sulfate

Heterogeneous OH Oxidation of Isoprene Epoxydiol-Derived Organosulfates: Kinetics, Chemistry and Formation of Inorganic Sulfate

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