Sulfate Formation via Cloud Processing from Isoprene Hydroxyl Hydroperoxides (ISOPOOH)

Dovrou, Eleni; Rivera-Rios, Jean C.; Bates, Kelvin H.; Keutsch, Frank N.

doi:10.1021/acs.est.9b04645

Cited by 41 publications

(83 citation statements)

References 47 publications

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“…Using model simulations, Bonn et al (2004) found organic hydroperoxides can account for up to 60% of global SOA. The aqueous phase reaction kinetics between organic peroxides and dissolved SO2 have been explored in previous studies (Lind et al, 1987;Gunz and Hoffmann, 1990;Dovrou et al, 2019;Yao et al, 2019). The second order reaction rate constants for organic peroxides in SOA (Dovrou et al, 2019;Yao et al, 2019) and S(IV) were measured to be on the order of 10 2 -10 3 M -1 s -1 , which are within the range of those measured for commercially available organic peroxides and small organic peroxides (Lind et al, 1987).…”

Section: Introductionsupporting

confidence: 57%

“…The aqueous phase reaction kinetics between organic peroxides and dissolved SO2 have been explored in previous studies (Lind et al, 1987;Gunz and Hoffmann, 1990;Dovrou et al, 2019;Yao et al, 2019). The second order reaction rate constants for organic peroxides in SOA (Dovrou et al, 2019;Yao et al, 2019) and S(IV) were measured to be on the order of 10 2 -10 3 M -1 s -1 , which are within the range of those measured for commercially available organic peroxides and small organic peroxides (Lind et al, 1987). Yao et al (2019) quantified the reactive uptake coefficient of SO2 (γSO2) onto α-pinene SOA to be on the order of 10 -4 -10 -3 , which is positively dependent on RH and inferred particle-phase peroxide content.…”

Section: Introductionmentioning

confidence: 99%

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Heterogeneous Interactions between SO2 and Organic Peroxides in Submicron Aerosol

Wang¹,

Liu²,

Jang³

et al. 2020

Preprint

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Abstract. Atmospheric models often underestimate particulate sulfate, a major component in ambient aerosol, suggesting missing sulfate formation mechanisms in the models. Heterogeneous reactions between SO2 and aerosol play an important role in particulate sulfate formation and its physicochemical evolution. Here we study the reactive uptake kinetics of SO2 onto aerosol containing organic peroxides. We present chamber studies of SO2 reactive uptake performed under different relative humidities (RH), particulate peroxide contents, peroxide types, and aerosol acidities. Using different model organic peroxides mixed with ammonium sulfate particles, SO2 uptake coefficient (γSO2) was found to be exponentially dependent on RH. γSO2 increases from 10−3 at RH 25 % to 10−2 at RH 71 % as measured for a multifunctional organic peroxide. Under similar conditions, the kinetics were found to be structurally dependent: multifunctional organic peroxides have a higher γSO2 than those with only one peroxide group, consistent with the reactivity trend observed previously in the aqueous phase. In addition, γSO2 is linearly related to particle-phase peroxide content, which in turn depends on gas-particle partitioning of organic peroxides. Aerosol acidity plays a complex role in determining SO2 uptake rate, influenced by the effective Henry's Law constant of SO2 and the condensed phase kinetics of the peroxide-SO2 reaction in the highly concentrated aerosol phase. These uptake coefficients are consistently higher than those calculated from the reaction kinetics in the bulk aqueous phase, and we show experimental evidence suggesting that other factors, such as particle-phase ionic strength, can play an essential role in determining the uptake kinetics. γSO2 for different types of secondary organic aerosol (SOA) were measured to be on the order of 10−4. Overall, this study provides quantitative evidence of the multiphase reactions between SO2 and organic peroxides, highlighting the important factors that govern the uptake kinetics.

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Section: Introductionsupporting

confidence: 57%

Section: Introductionmentioning

confidence: 99%

Heterogeneous Interactions between SO2 and Organic Peroxides in Submicron Aerosol

Wang¹,

Liu²,

Jang³

et al. 2020

Preprint

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“…Having Henry's law constants on the order of 10 5 M • atm −1 , ISOPOOH isomers can partition into cloud and fog water and participate in condensed-phase reactions (Rivera-Rios, 2018). Dovrou et al (2019b) showed that ISOPOOH oxidizes sulfur dioxide (SO2,aq) in cloud and fog water, producing sulfate (SO 4 2− ). Aqueous hydrogen peroxide (H 2 O 2 ) oxidizes SO2,aq to sulfate with a 100% yield with a rate constant that increases with decreasing pH (Lind et al, 1987).…”

Section: Introductionmentioning

confidence: 99%

Towards a Chemical Mechanism of the Oxidation of Aqueous Sulfur Dioxide via Isoprene Hydroxyl Hydroperoxides (ISOPOOH)

Dovrou¹,

Bates²,

Rivera-Rios³

et al. 2021

Preprint

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Abstract. In-cloud chemistry has important ramifications for atmospheric particulate matter formation and gas-phase chemistry. Recent work has shown that, like hydrogen peroxide (H2O2), the two main isomers of isoprene hydroxyl hydroperoxide (ISOPOOH) oxidize sulfur dioxide dissolved in cloud droplets (SO2,aq) to sulfate. The work revealed that the pathway of SO2,aq oxidation with ISOPOOH differs from that of H2O2. We investigate the chemical mechanisms of oxidation of SO2,aq with ISOPOOH in the cloud-relevant pH range of 3–6 and compare them with the previously reported mechanisms of oxidation of SO2,aq with H2O2, methyl hydroperoxide and peroxyacetic acid. The organic products of the reaction are identified and two pathways are proposed. For 1,2-ISOPOOH, a higher yield pathway via proposed radical intermediates yields methyl vinyl ketone (MVK) and formaldehyde, which can react to hydroxymethanesulfonate (HMS) when SO2,aq is present. A lower yield non-fragmentation oxygen addition pathway is proposed that results in formation of isoprene-derived diols (ISOPOH). Based on global simulations, this mechanism is not a significant pathway for formation of MVK and formaldehyde relative to their gas-phase formation but, as previously reported, it can be regionally important for sulfate production. The study adds to previous work that highlights similarities and differences between gas-phase and cloud-droplet processing of reactive organic carbon.

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“…the aqueous oxidation of S(IV) by HCHO and hydroxyl hydroperoxide (ISOPOOH) to form hydroxy-methane sulfonate (HMS) and sulfate (Moch et al, 2018;Dovrou et al, 2019), can also explain the sulfate underestimation even though the cloud water has already been corrected. In addition, cloud constraints are based on the MODIS LWP, which has been reported with an uncertainty range of ±30 % (Dong et al, 2008;Min et al, 2012;Khanal et al, 2018).…”

Section: Impact Of Cloud Constraint On Snamentioning

confidence: 99%

“…CC BY 4.0 License. Salzen, 2006;Harris et al, 2013;Kim et al, 2015;Ervens et al, 2018b;Dovrou et al, 2019). The aqueous formation rate depends on liquid water content (LWC), the size distribution, pH and lifetime of cloud droplets, as well as the availability of oxidants.…”

Section: Introductionmentioning

confidence: 99%

Improvement of inorganic aerosol component in PM2.5 by constraining aqueous-phase formation of sulfate in cloud with satellite retrievals: WRF-Chem simulations

Sha

Wang

et al. 2020

Preprint

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Abstract. High concentrations of PM2.5 in China have caused severe visibility degradation and health problem. However, it is still a big challenge to accurately predict PM2.5 and its chemical components in the numerical model. In this study, we compared the inorganic aerosol components of PM2.5 (sulfate, nitrate, and ammonium (SNA)) simulated by WRF-Chem with in-situ data during a heavy haze-fog event (November 2018) in Nanjing. The comparisons show that the model underestimates the sulfate concentrations by 81 % and fails to reproduce the significant increase of sulfate concentrations from early morning to noon, which corresponds to the timing of fog dissipation, suggesting that the model underestimates the aqueous-phase formation of sulfate in clouds. In addition, the model overestimates both nitrate and ammonium concentrations by 184 % and 57 %, respectively. These ultimately result in the simulated SNA 77.2 % higher than the observations. However, as the important aqueous-phase reactors, cloud water are simultaneously underestimated by the model. Therefore, the modeled cloud water was constrained based on the MODIS Liquid Water Path (LWP) observations. Results show that the simulation with MODIS-corrected cloud water amount increases the sulfate by a factor of 3, decreases NMB by 53.5 %, and can reproduce its diurnal cycles, i.e. the peak concentration at noon. Also, the model absolute bias of nitrate decreases from 184 % to 50 %, especially for the nocturnal concentrations, which suggests the MODIS-constrained simulation improved the diurnal pattern. Although the simulated ammonium is still higher than the observation, corrected cloud water lead to the decrease of the modeled bias of SNA from 77.2 % to 14.1 %. The strong sensitivity of simulated SNA concentration to the cloud water provides an explanation for the bias of SNA simulation. Hence, the uncertainties of cloud water can lead to model bias in simulating SNA, and can be reduced by constraining the model with satellite observations.

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Sulfate Formation via Cloud Processing from Isoprene Hydroxyl Hydroperoxides (ISOPOOH)

Cited by 41 publications

References 47 publications

Heterogeneous Interactions between SO<sub>2</sub> and Organic Peroxides in Submicron Aerosol

Heterogeneous Interactions between SO<sub>2</sub> and Organic Peroxides in Submicron Aerosol

Towards a Chemical Mechanism of the Oxidation of Aqueous Sulfur Dioxide via Isoprene Hydroxyl Hydroperoxides (ISOPOOH)

Improvement of inorganic aerosol component in PM<sub>2.5</sub> by constraining aqueous-phase formation of sulfate in cloud with satellite retrievals: WRF-Chem simulations

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Sulfate Formation via Cloud Processing from Isoprene Hydroxyl Hydroperoxides (ISOPOOH)

Cited by 41 publications

References 47 publications

Heterogeneous Interactions between SO&lt;sub&gt;2&lt;/sub&gt; and Organic Peroxides in Submicron Aerosol

Heterogeneous Interactions between SO&lt;sub&gt;2&lt;/sub&gt; and Organic Peroxides in Submicron Aerosol

Towards a Chemical Mechanism of the Oxidation of Aqueous Sulfur Dioxide via Isoprene Hydroxyl Hydroperoxides (ISOPOOH)

Improvement of inorganic aerosol component in PM&lt;sub&gt;2.5&lt;/sub&gt; by constraining aqueous-phase formation of sulfate in cloud with satellite retrievals: WRF-Chem simulations

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Heterogeneous Interactions between SO<sub>2</sub> and Organic Peroxides in Submicron Aerosol

Heterogeneous Interactions between SO<sub>2</sub> and Organic Peroxides in Submicron Aerosol

Improvement of inorganic aerosol component in PM<sub>2.5</sub> by constraining aqueous-phase formation of sulfate in cloud with satellite retrievals: WRF-Chem simulations