Joint Impacts of Acidity and Viscosity on the Formation of Secondary Organic Aerosol from Isoprene Epoxydiols (IEPOX) in Phase Separated Particles

Zhang, Yue; Chen, Yuzhi; Lei, Ziying; Olson, Nicole E.; Riva, Matthieu; Koss, A.; Zhang, Zhenfa; Gold, Avram; Jayne, John T.; Worsnop, Douglas R.; Onasch, T. B.; Kroll, J. H.; Turpin, Barbara J.; Ault, Andrew P.; Surratt, Jason D.

doi:10.1021/acsearthspacechem.9b00209

Cited by 82 publications

(162 citation statements)

References 105 publications

Supporting

Mentioning

153

Contrasting

Order By: Relevance

“…The particle‐phase sulfate exhibited higher levels during winter (maximum 32.6 μg m −3 in winter vs 19.6 μg m −3 in summer), which would promote the formation of C 10 H 16 NO 7 S − (Worton et al, 2011). An increase for aerosol acidity in winter would enhance OS formation (Gaston et al, 2014; Zhang et al, 2019). Lower ambient temperatures in winter would enhance the condensation of intermediates onto particles (Sheehan & Bowman, 2001) and subsequently promote the reaction with sulfates on acidic particles to form C 10 H 16 NO 7 S − .…”

Section: Resultsmentioning

confidence: 99%

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

et al. 2020

View full text Add to dashboard Cite

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.

show abstract

Section: Resultsmentioning

confidence: 99%

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

et al. 2020

View full text Add to dashboard Cite

show abstract

“…Recent studies have shown that the phase state and viscosity of the particles, depending on the particle composition and environmental factors, can significantly affect the diffusivity of organic molecules, water molecules and oxidants such as gas-phase OH radicals, which in turn affect the overall oxidation rate and formation of products (Chan et al, 2014;Slade and Knopf, 2014;Chim et al, 2017b;Marshall et al, 2016Marshall et al, , 2018. Isoprene-derived SOA, especially when formed in the presence of acidic sulfate particles, have been reported to be highly viscous (Shrivastava et al, 2017;Zhang et al, 2019). For instance, Riva et al (2019) have shown that a viscous IEPOX-SOA coating was likely formed in the presence of acidic sulfate seed particles.…”

Section: Conclusion and Atmospheric Implicationsmentioning

confidence: 99%

“…To date, the heterogeneous kinetics and chemistry of many pure organic compounds or organic mixtures have been investigated (Zhang et al, 2015;Enami et al, 2016;Socorro et al, 2017;Marshall et al, 2018;Zhao et al, 2019). There remains large uncertainty in how inorganic salts alter the heterogeneous kinetics and chemistry of organic compounds (McNeill et al, 2007(McNeill et al, , 2008Dennis-Smither et al, 2012).…”

Section: Introductionmentioning

confidence: 99%

Effect of inorganic-to-organic mass ratio on the heterogeneous OH reaction rates of erythritol: implications for atmospheric chemical stability of 2-methyltetrols

Lam

Wilson

et al. 2020

Atmos. Chem. Phys.

View full text Add to dashboard Cite

Abstract. The 2-methyltetrols have been widely chosen as chemical tracers for isoprene-derived secondary organic aerosols. While they are often assumed to be relatively unreactive, a laboratory study reported that pure erythritol particles (an analog of 2-methyltetrols) can be heterogeneously oxidized by gas-phase OH radicals at a significant rate. This might question the efficacy of these compounds as tracers in aerosol source-apportionment studies. Additional uncertainty could arise as organic compounds and inorganic salts often coexist in atmospheric particles. To gain more insights into the chemical stability of 2-methyltetrols in atmospheric particles, this study investigates the heterogeneous OH oxidation of pure erythritol particles and particles containing erythritol and ammonium sulfate (AS) at different dry inorganic-to-organic mass ratios (IOR) in an aerosol flow tube reactor at a high relative humidity of 85 %. The same reaction products are formed upon heterogenous OH oxidation of erythritol and erythritol–AS particles, suggesting that the reaction pathways are not strongly affected by the presence and amount of AS. On the other hand, the effective OH uptake coefficient, γeff, is found to decrease by about a factor of ∼20 from 0.45±0.025 to 0.02±0.001 when the relative abundance of AS increases and the IOR increases from 0.0 to 5.0. One likely explanation is the presence of dissolved ions slows down the reaction rates by decreasing the surface concentration of erythritol and reducing the frequency of collision between erythritol and gas-phase OH radicals at the particle surface. Hence, the heterogeneous OH reactivity of erythritol and likely 2-methyltetrols in atmospheric particles would be slower than previously thought when the salts are present. Given 2-methyltetrols often coexist with a significant amount of AS in many environments, where ambient IOR can vary from ∼1.89 to ∼250, our kinetic data would suggest that 2-methyltetrols in atmospheric particles are likely chemically stable against heterogeneous OH oxidation under humid conditions.

show abstract

“…À2 Pa s at these conditions (Supplementary Methods) 41,43,44 . These results suggest that organic particles containing a significant amount of 2-MT OSs remain in a glassy or semi-solid phase state at conditions requisite for depositional ice nucleation.…”

Section: Resultsmentioning

confidence: 99%

“…For instance, the formation of IEPOX-OSs is accompanied by the rapid depletion of inorganic sulfates. This reduces hygroscopicity and increases aerosol viscosity 41,44 , both of which are factors that could slow the uptake and diffusion of water into isoprene-derived SOA and potentially enhance their depositional ice nucleation properties.…”

Section: Resultsmentioning

confidence: 99%

A biogenic secondary organic aerosol source of cirrus ice nucleating particles

et al. 2020

Self Cite

View full text Add to dashboard Cite

Atmospheric ice nucleating particles (INPs) influence global climate by altering cloud formation, lifetime, and precipitation efficiency. The role of secondary organic aerosol (SOA) material as a source of INPs in the ambient atmosphere has not been well defined. Here, we demonstrate the potential for biogenic SOA to activate as depositional INPs in the upper troposphere by combining field measurements with laboratory experiments. Ambient INPs were measured in a remote mountaintop location at –46 °C and an ice supersaturation of 30% with concentrations ranging from 0.1 to 70 L–1. Concentrations of depositional INPs were positively correlated with the mass fractions and loadings of isoprene-derived secondary organic aerosols. Compositional analysis of ice residuals showed that ambient particles with isoprene-derived SOA material can act as depositional ice nuclei. Laboratory experiments further demonstrated the ability of isoprene-derived SOA to nucleate ice under a range of atmospheric conditions. We further show that ambient concentrations of isoprene-derived SOA can be competitive with other INP sources. This demonstrates that isoprene and potentially other biogenically-derived SOA materials could influence cirrus formation and properties.

show abstract

Joint Impacts of Acidity and Viscosity on the Formation of Secondary Organic Aerosol from Isoprene Epoxydiols (IEPOX) in Phase Separated Particles

Cited by 82 publications

References 105 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

Effect of inorganic-to-organic mass ratio on the heterogeneous OH reaction rates of erythritol: implications for atmospheric chemical stability of 2-methyltetrols

A biogenic secondary organic aerosol source of cirrus ice nucleating particles

Contact Info

Product

Resources

About