Parameterization of heterogeneous reaction of SO2 to sulfate on dust with coexistence of NH3 and NO2 under different humidity conditions

Zhang, Shuping; Xing, Jia; Sarwar, Golam; Ge, Yanli; He, Hong; Duan, Fengkui; Zhao, Yan; He, Kebin; Zhu, Lailai; Chu, Biwu

doi:10.1016/j.atmosenv.2019.04.004

Cited by 44 publications

(23 citation statements)

References 70 publications

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“…γSO2 increases with increased relative humidity, which could even be more significant under high RH regime. This is consistent with previous laboratory studies that measured the reactive uptake coefficient of SO2 onto aerosol to be exponentially dependent on RH (Zhang et al, 2019;Yao et al, 2019). Additionally, multiple field campaigns have observed significant correlation between particulate sulfate formation and ambient RH (Song et al, 2019;Sun et al, 2013;Huang et al, 2020 (Seinfeld and Pandis, 2012).…”

Section: So2 Uptake and Rhsupporting

confidence: 91%

“…2). The positive dependence of the reactive uptake coefficient of water-soluble gaseous species on RH has also been observed in other studies (Thornton et al, 2003;Griffiths et al, 2009;Zhao et al, 2017;Zhang et al, 2019). Recently, the uptake behavior of SO2 onto soot, mineral dust and SOA were also shown to positively depend on RH (Zhang et al, 2019;Zhao et al, 2017;Yao et al, 2019).…”

Section: So2 Uptake and Rhsupporting

confidence: 77%

“…The reactive uptake coefficient of SO2 onto Saharan mineral dust was reported on the order of -5 (Adams et al, 2005). γSO2 onto dust with the coexistence of NO2 and NH3 under various RH conditions were measured to be -7 to 10 -5 (Zhang et al, 2019). For a variety of metal oxides, SO2 reactive uptake coefficients were quantified to be between 10 -6 and 10 -4 (Usher et al, 2002;Fu et al, 2007;Shang et al, 2010).…”

Section: So2 Uptake Onto Soamentioning

confidence: 99%

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Heterogeneous Interactions between SO<sub>2</sub> 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: So2 Uptake and Rhsupporting

confidence: 91%

Section: So2 Uptake and Rhsupporting

confidence: 77%

Section: So2 Uptake Onto Soamentioning

confidence: 99%

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

Wang¹,

Liu²,

Jang³

et al. 2020

Preprint

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“…Although SO2 concentrations are linearly related to SO2 emissions, the chemical transport model overestimates SO2 concentrations and underestimates SO4 2concentrations due to large uncertainties in simulating the rapid conversion of SO2 to SO4 2during haze episodes (Zhang et al, 2019). To address this https://doi.org/10.5194/acp-2020-522 Preprint.…”

Section: Based On Our Previous Knowledge Of Emission-concentration Rementioning

confidence: 99%

Quantifying the emission changes and associated air quality impacts during the COVID-19 pandemic in North China Plain: a response modeling study

Xing¹,

Li²,

Jiang³

et al. 2020

Preprint

Self Cite

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Abstract. Quantification of emission changes is a prerequisite for the assessment of control effectiveness in improving air quality. However, the traditional bottom-up method for characterizing emissions requires detailed investigation of emissions data (e.g., activity and other emission parameters) that usually takes months to perform and limits timely assessments. Here we propose a novel method to address this issue by using a response model that provides real-time estimation of emission changes based on air quality observations in combination with emission-concentration response functions derived from chemical transport modeling. We applied the new method to quantify the emission changes in the North China Plain (NCP) due to the COVID-19 pandemic shutdown, which overlapped the Spring Festival holiday. Results suggest that the anthropogenic emissions of NO2, SO2, VOC, and primary PM2.5 in NCP were reduced by 51 %, 28 %, 67 % and 63 %, respectively, due to the COVID-19 shutdown, indicating longer and stronger shutdown effects in 2020 compared to the previous Spring Festival holiday. The reductions of VOC and primary PM2.5 emissions are generally effective in reducing O3 and PM2.5 concentrations. However, such air quality improvements are largely offset by reductions in NOx emissions. NOx emission reductions lead to increases in O3 and PM2.5 concentrations in NCP due to the strongly VOC-limited conditions in winter. A strong NH3-rich condition is also suggested from the air quality response to the substantial NOx emission reduction. Well-designed control strategies are recommended based on the air quality response associated with the unexpected emission changes during the COVID-19 period. In addition, our results demonstrate that the new response-based inversion model can well capture emission changes based on variations in ambient concentrations, and thereby illustrate the great potential for improving the accuracy and efficiency of bottom-up emission inventory methods.

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“…There is also evidence for heterogeneous SO 2 oxidation on existing low pH aerosol surfaces and RH-dependent parameterizations have been applied to reproduce the observed high concentrations of sulfate [39,353]. Reactive uptake of SO 2 onto mineral dust particles dependent on NH 3 , NO 2 and RH has been modeled by Zhang et al [354]. Shao et al [355] parameterize aqueous-phase S(IV) oxidation in wintertime haze aerosols in Beijing, China, by various oxidants such as H 2 O 2 , O 3 , NO 2 and O 2 catalyzed by transition metal ions and conclude that transition metal ion chemistry is important.…”

Section: Inorganic Aerosol Chemistrymentioning

confidence: 99%

Current State of Atmospheric Aerosol Thermodynamics and Mass Transfer Modeling: A Review

Semeniuk

Dastoor

2020

Atmosphere

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A useful aerosol model must be able to adequately resolve the chemical complexity and phase state of the wide particle size range arising from the many different secondary aerosol growth processes to assess their environmental and health impacts. Over the past two decades, significant advances in understanding of gas-aerosol partitioning have occurred, particularly with respect to the role of organic compounds, yet aerosol representations have changed little in air quality and climate models since the late 1990s and early 2000s. The gas-aerosol partitioning models which are still commonly used in air quality models are separate inorganics-only thermodynamics and secondary organic aerosol (SOA) formation based on absorptive partitioning theory with an assumption of well-mixed liquid-like particles that continuously maintain equilibrium with the gas phase. These widely used approaches in air quality models for secondary aerosol composition and growth based on separated inorganic and organic processes are inadequate. This review summarizes some of the important developments during the past two decades in understanding of gas aerosol mass transfer processes. Substantial increases in computer performance in the last decade justify increasing the process detail in aerosol models. Organics play a central role during post-nucleation growth into the accumulation mode and change the hygroscopic properties of sulfate aerosol. At present, combined inorganic-organic aerosol thermodynamics models are too computationally expensive to be used online in 3-D simulations without high levels of aggregation of organics into a small number of functional surrogates. However, there has been progress in simplified modeling of liquid-liquid phase separation (LLPS) and distinct chemical regimes within organic-rich and inorganic-rich phases. Additional limitations of commonly used thermodynamics models are related to lack of surface tension data for various aerosol compositions in the small size limit, and lack of a comprehensive representation of surface interaction terms such as disjoining pressure in the Gibbs free energy which become significant in the small size limit and which affect both chemical composition and particle growth. As a result, there are significant errors in modeling of hygroscopic growth and phase transitions for particles in the nucleation and Aitken modes. There is also increasing evidence of reduced bulk diffusivity in viscous organic particles and, therefore, traditional secondary organic aerosol models, which are typically based on the assumption of instantaneous equilibrium gas-particle partitioning and neglect the kinetic effects, are no longer tenable.

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Parameterization of heterogeneous reaction of SO2 to sulfate on dust with coexistence of NH3 and NO2 under different humidity conditions

Cited by 44 publications

References 70 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

Quantifying the emission changes and associated air quality impacts during the COVID-19 pandemic in North China Plain: a response modeling study

Current State of Atmospheric Aerosol Thermodynamics and Mass Transfer Modeling: A Review

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Parameterization of heterogeneous reaction of SO2 to sulfate on dust with coexistence of NH3 and NO2 under different humidity conditions

Cited by 44 publications

References 70 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

Quantifying the emission changes and associated air quality impacts during the COVID-19 pandemic in North China Plain: a response modeling study

Current State of Atmospheric Aerosol Thermodynamics and Mass Transfer Modeling: A Review

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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