Reactive Uptake of Isoprene Epoxydiols Increases the Viscosity of the Core of Phase-Separated Aerosol Particles

Olson, Nicole E.; Lei, Ziying; Craig, R. L.; Zhang, Yue; Chen, Yuzhi; Lambe, Andrew T.; Zhang, Zhenfa; Gold, Avram; Surratt, Jason D.; Ault, Andrew P.

doi:10.1021/acsearthspacechem.9b00138

Cited by 44 publications

(110 citation statements)

References 123 publications

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“…Thus, it is expected to be nonvolatile and likely remains in the particle phase. Additionally, the structure-activity relationship (SAR) model developed for the decomposition of alkoxy radicals suggests that the formation of the larger fragmentation product (i.e., C 3 carboxylic acid) is more kinetically favorable than that of the smaller fragmentation product (i.e., C 2 hydroxyketone) upon decomposition, as the formation rate coefficient (k SAR ) of the C 3 fragmentation product is 7.13 × 10 12 s −1 , which is about 3 orders of magnitude higher than that of the C 2 fragmentation product (3.40 × 10 9 s −1 ) (Peeters et al, 2004;Vereecken et al, 2009).…”

Section: Fragmentation Productsmentioning

confidence: 97%

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.

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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.

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Section: Fragmentation Productsmentioning

confidence: 97%

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.

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“…ALWC has dual effects on OS formation. On one hand, elevated ALWC can reduce the viscosity and/or inhibit the liquid-liquid phase separation of aerosols, which would favor the dissolution and mixing of reactive intermediates such as IEPOX and multifunctional aldehydes in aqueous sulfate aerosols (Shiraiwa et al, 2011;Liao et al, 2015;McNeill et al, 2012) or SO 2 in organic aerosols (Shang et al, 2016;Passananti et al, 2016;Yao et al, 2019), thereby enhancing OS formation. On the other hand, high ALWC would decrease aerosol acidity via dilution, hence inhibiting acid-catalyzed OS formation.…”

Section: Introductionmentioning

confidence: 99%

Organosulfates in atmospheric aerosols in Shanghai, China: seasonal and interannual variability, origin, and formation mechanisms

et al. 2021

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Abstract. Organosulfates (OSs) are ubiquitous in the atmosphere and serve as important tracers for secondary organic aerosols (SOAs). Despite intense research over the years, the abundance, origin, and formation mechanisms of OSs in ambient aerosols, particularly in regions with severe anthropogenic pollution, are still not well understood. In this study, we collected filter samples of ambient fine particulate matter (PM2.5) over four seasons in both 2015–2016 and 2018–2019 at an urban site in Shanghai, China, and comprehensively characterized the OS species in these PM2.5 samples using an ultra-performance liquid chromatography quadrupole time-of-flight mass spectrometer equipped with an electrospray ionization (ESI) source (UPLC-ESI-QToFMS). Overall, we find that while the concentration of organic aerosols (OAs) decreased by 29 % in 2018–2019 compared to that in 2015–2016, mainly as a result of the reduction of anthropogenic pollutant emissions in eastern China, the annually averaged concentrations of 35 quantified OSs were similar in both years (65.5 ± 77.5 ng m−3, 0.57 % ± 0.56 % of OA in 2015–2016 vs. 59.4 ± 79.7 ng m−3, 0.66 % ± 0.56 % of OA in 2018–2019), suggesting an increased contribution of SOAs to OAs in 2018–2019 compared to 2015–2016. Isoprene- and monoterpene-derived OSs were the two most abundant OS families, on average, accounting for 36.3 % and 31.0 % of the quantified OS concentrations, respectively, during both sampling years, suggesting an important contribution of biogenic emissions to the production of OSs and SOAs in Shanghai. The abundance of biogenic OSs, particularly those arising from isoprene, exhibited strong seasonality (peaked in summer) but no significant interannual variability. In contrast, the quantified anthropogenic OSs had little seasonal variability and declined in 2018–2019 compared with those in 2015–2016. The C2 and C3 OS species that have both biogenic and anthropogenic origins contributed, on average, 19.0 % of the quantified OSs, with C2H3O6S−, C3H5O5S−, and C3H5O6S− being the most abundant species, together accounting for 76 % of the C2 and C3 OS concentrations in 2015–2016 and 2018–2019. 2-Methyltetrol sulfate (2-MTS, C5H11O7S−) and monoterpene-derived C10H16NO7S− were the most abundant OSs and nitrooxy OSs in summer, on average, contributing 31 % and 5 % of the quantified OSs, respectively, during the summertime of the sampling years. The substantially larger concentration ratio of 2-MTS to 2-methylglyceric acid sulfate (2-MAS, C4H7O7S−) in summer (6.8–7.8) compared to the other seasons (0.31–0.78) implies that low-NOx oxidation pathways played a dominant role in isoprene-derived SOA formation in summer, while high-NOx reaction pathways were more important in other seasons. We further find that the production of OSs was largely controlled by the level of Ox (Ox= O3+ NO2), namely the photochemistry of OS precursors, particularly in summer, though sulfate concentration, aerosol acidity, and aerosol liquid water content (ALWC) that could affect the heterogeneous chemistry of reactive intermediates leading to OS formation also played a role. Our study provides valuable insights into the characteristics and mechanisms of OS formation in a typical Chinese megacity and implies that the mitigation of Ox pollution can effectively reduce the production of OSs and SOAs in eastern China.

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“…It has been estimated that OS accounted for 6-12% of total sulfur in a rural area in K-puszta, Hungary (Lukacs et al, 2009), 1.3% of fine particulate organic mass (POM) in Fairbanks, Alaska (Shakya and Peltier, 2013), and 1-13% of fine POM across the continental United States (Tolocka and Turpin, 2012;Shakya and Peltier, 2015). Studies have also shown that OS can affect aerosol properties such as acidity, viscosity, hygroscopicity, and light-absorbing properties (Nguyen et al, 2012;Hansen et al, 2015;Estillore et al, 2016;DeRieux et al, 2018;Fleming et al, 2019;Olson et al, 2019;Riva et al, 2019).…”

Section: Introductionmentioning

confidence: 99%

Organosulfates in atmospheric aerosols in Shanghai, China: seasonal and interannual variability, origin, and formation mechanisms

Wang¹,

Zhao²,

Wang³

et al. 2020

Preprint

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Abstract. Organosulfates (OS) are ubiquitous in the atmosphere and serve as important tracers for secondary organic aerosols (SOA). Despite intense research over years, the abundance, origin, and formation mechanisms of OS in ambient aerosols, in particular in regions with severe anthropogenic pollution, are still not well understood. In this study, we collected filter samples of ambient fine particulate matter (PM2.5) over four seasons in both 2015/2016 and 2018/2019 at an urban site in Shanghai, China, and comprehensively characterized the OS species in these PM2.5 samples using a liquid chromatography coupled to a high resolution mass spectrometer (UPLC-ESI-QToF-MS). We find that while the concentration of organic aerosol (OA) decreased by 29 % in 2018/2019, compared to that in 2015/2016, the annually averaged concentrations of 35 quantified OS were similar in two years (65.5 ± 77.5 ng m−3 in 2015/2016 versus 59.4 ± 79.7 ng m−3 in 2018/2019), suggesting an increased contribution of SOA to OA in 2018/2019 than in 2015/2016. Isoprene- and monoterpene-derived OS are the two most abundant OS families, on average accounting for 36.3 % and 31.0 % of the quantified OS concentrations, respectively, suggesting an important contribution of biogenic emissions to the production of OS and SOA in Shanghai. The abundance of biogenic OS, particularly those arising from isoprene, exhibited strong seasonality (peaked in summer) but no significant interannual variability. In contrast, anthropogenic OS such as diesel-derived ones had little seasonal variability and declined obviously in 2018/2019 compared with that in 2015/2016. This reflects a significant change in precursor emissions in eastern China in recent years. The C2/C3 OS species that have both biogenic and anthropogenic origins averagely contributed to 19.0 % of the quantified OS, with C2H3O6S−, C3H5O5S−, and C3H5O6S− being the most abundant ones, together accounting for 76 % of C2/C3 OS concentrations. 2-Methyltetrol sulfate (2-MT-OS, C5H11O7S−) and monoterpene-derived C10H16NO7S− were the most abundant OS and nitrooxy-OS in summer, contributing to 31 % and 5 % of the quantified OS, respectively. The substantially larger concentration ratio of 2-MT-OS to 2-methylglyceric acid sulfate (2-MA-OS, C4H7O7S−) in summer (6.8–7.8) than in other seasons (0.31–0.78) implies that low-NOx oxidation pathways played a dominant role in isoprene-derived SOA formation in summer, while high-NOx reaction pathways were more important in other seasons. We further find that the production of OS was largely controlled by the level of Ox (Ox = O3 + NO2), namely, the photochemistry of OS precursors, in particular in summer, though sulfate concentration, aerosol acidity, as well as aerosol liquid water content (ALWC) that could affect the heterogeneous chemistry of reactive intermediates leading to OS formation also played a role. Our study provides valuable insights into the characteristics and mechanisms of OS formation in a typical Chinese megacity and implies that mitigation of Ox pollution can effectively reduce the production of OS and SOA in eastern China.

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Reactive Uptake of Isoprene Epoxydiols Increases the Viscosity of the Core of Phase-Separated Aerosol Particles

Cited by 44 publications

References 123 publications

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

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

Organosulfates in atmospheric aerosols in Shanghai, China: seasonal and interannual variability, origin, and formation mechanisms

Organosulfates in atmospheric aerosols in Shanghai, China: seasonal and interannual variability, origin, and formation mechanisms

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