Sulfate formation is dominated by manganese-catalyzed oxidation of SO2 on aerosol surfaces during haze events

Wang, Weigang; Liu, Mingyuan; Wang, Tiantian; Song, Yu; Zhou, Li; Cao, Junji; Hu, Jingnan; Tang, Guigang; Chen, Zhe; Li, Zhijie; Xu, Zhenying; Peng, Chao; Lian, Chaofan; Yan, Chuanwei; Pan, Yuepeng; Zhang, Yunhong; Sun, Yele; Li, Weijun; Zhu, Tong; Tian, Hongyu; Ge, Maofa

doi:10.1038/s41467-021-22091-6

Cited by 172 publications

(238 citation statements)

References 73 publications

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“…3a, the PM 2.5 concentration was more than an order of magnitude lower in samples from Hyytiälä than in those from Beijing (∼ 5 and ∼ 200 µg m −3 , respectively), and the volume-specific yields of aqueousphase H 2 O 2 exhibited a similarly large difference (∼ 10 and ∼ 200 µg m −3 , respectively), while the volume-specific yields of aqueous-phase radicals exhibited a much smaller difference (∼ 3 and ∼ 7 pmol m −3 , respectively; Tables S1, S4, and S5). The strong increase in H 2 O 2 with increasing PM 2.5 concentration is consistent with earlier studies identifying a wide range of redox-active organic and inorganic aerosol components that can produce H 2 O 2 in the aqueous phase (Gunz and Hoffmann, 1990;Anastasio et al, 1994;Zuo and Deng, 1997;Arellanes et al, 2006;Chung et al, 2006;Hua et al, 2008;Möller, 2009;Wang et al, 2010Wang et al, , 2012Anglada et al, 2015;Herrmann et al, 2015;Lakey et al, 2016;Tong et al, 2018;Bianco et al, 2020).…”

Section: Yields Of Aqueous-phase Radicals and H 2 O 2 Fromsupporting

confidence: 90%

Aqueous-phase reactive species formed by fine particulate matter from remote forests and polluted urban air

et al. 2021

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Abstract. In the aqueous phase, fine particulate matter can form reactive species (RS) that influence the aging, properties, and health effects of atmospheric aerosols. In this study, we explore the RS yields of aerosol samples from a remote forest (Hyytiälä, Finland) and polluted urban locations (Mainz, Germany; Beijing, China), and we relate the RS yields to different chemical constituents and reaction mechanisms. Ultra-high-resolution mass spectrometry was used to characterize organic aerosol composition, electron paramagnetic resonance (EPR) spectroscopy with a spin-trapping technique was applied to determine the concentrations of ⚫OH, O2⚫-, and carbon- or oxygen-centered organic radicals, and a fluorometric assay was used to quantify H2O2. The aqueous H2O2-forming potential per mass unit of ambient PM2.5 (particle diameter < 2.5 µm) was roughly the same for all investigated samples, whereas the mass-specific yields of radicals were lower for sampling sites with higher concentrations of PM2.5. The abundances of water-soluble transition metals and aromatics in ambient PM2.5 were positively correlated with the relative fraction of ⚫OH and negatively correlated with the relative fraction of carbon-centered radicals. In contrast, highly oxygenated organic molecules (HOM) were positively correlated with the relative fraction of carbon-centered radicals and negatively correlated with the relative fraction of ⚫OH. Moreover, we found that the relative fractions of different types of radicals formed by ambient PM2.5 were comparable to surrogate mixtures comprising transition metal ions, organic hydroperoxide, H2O2, and humic or fulvic acids. The interplay of transition metal ions (e.g., iron and copper ions), highly oxidized organic molecules (e.g., hydroperoxides), and complexing or scavenging agents (e.g., humic or fulvic acids) leads to nonlinear concentration dependencies in aqueous-phase RS production. A strong dependence on chemical composition was also observed for the aqueous-phase radical yields of laboratory-generated secondary organic aerosols (SOA) from precursor mixtures of naphthalene and β-pinene. Our findings show how the composition of PM2.5 can influence the amount and nature of aqueous-phase RS, which may explain differences in the chemical reactivity and health effects of particulate matter in clean and polluted air.

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Section: Yields Of Aqueous-phase Radicals and H 2 O 2 Fromsupporting

confidence: 90%

Aqueous-phase reactive species formed by fine particulate matter from remote forests and polluted urban air

et al. 2021

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“…The ƒatom signal of N decreased during the haze periods (Ep3: 21%, clean period: 29%) while S increased (Ep3: 1.4%, clean period: 0.67%), consistent with the CHON and CHOS group fraction variations (shown in Figure 2(a)). Although the mechanism of organosulfur and inorganic sulfate formation in heterogeneous reactions is not fully understood, it seems probable that SO2 is rapidly oxidized and sulfate/organosulfur is formed in aerosol water with different types of oxidants and catalysts (Song et al, 2018;Cheng et al, 2016b;Liu et al, 2020a;Wang et al, 2021b).…”

Section: Molecular Composition Of Oamentioning

confidence: 99%

Influence of organic aerosol composition determined by offline FIGAERO-CIMS on particle absorptive properties in autumn Beijing

Cai

Wang

et al. 2021

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Abstract. Organic aerosol (OA) is a major component of fine particulate matter (PM) affecting air quality, human health, and the climate. The absorptive and reflective behavior of OA components contributes to determining particle optical properties and thus their effects on the radiative budget of the troposphere. There is limited knowledge on the influence of the molecular composition of OA on particle optical properties in the polluted urban environment. In this study, we characterized the molecular composition of oxygenated OA collected on filter samples in autumn of 2018 in Beijing, China, with a filter inlet for gases and aerosols coupled to a high-resolution time-of-flight chemical ionization mass spectrometer (FIGAERO-CIMS). Three haze episodes occurred during our sampling period with daily maximum concentrations of OA of 50, 30, and 55 µg m−3, respectively. We found that the signal intensities of dicarboxylic acids and sulfur-containing compounds increased during the two more intense haze episodes, while the relative contributions of wood-burning markers and other aromatic compounds were enhanced during the cleaner periods. We further assessed the optical properties of oxygenated OA components by combining the detailed chemical composition measurements with collocated particle light absorption measurements. We show that light-absorption enhancement (Eabs) of black carbon (BC) was mostly related to more oxygenated OA (e.g. dicarboxylic acids), likely formed in aqueous-phase reactions during the intense haze periods with higher relative humidity, and speculate that they might contribute to lensing effects. Aromatics and nitro-aromatics (e.g. nitrocatechol and its derivatives) were mostly related to a high light absorption coefficient (babs) consistent with light-absorbing (brown) carbon (BrC). Our results provide information on oxygenated OA components at the molecular level associated with BrC and BC particle light-absorption and can serve as a basis for further studies on the effects of anthropogenic OA on radiative forcing in the urban environment.

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“…Modeling studies greatly underestimated (∼ 54 %) SO 2− 4 concentration in serve pollution events in Beijing if only considering gas-phase oxidation of SO 2 , while the normalized mean bias (NMB) decreased significantly after heterogeneous oxidation of SO 2 being considered (Zheng et al, 2015). Several heterogeneous and/or multiphase oxidation pathways, such as oxidation of SO 2 or sulfite by H 2 O 2 (Huang et al, 2015;Maaß et al, 1999;Ye et al, 2021;Liu et al, 2021), HONO (J. F. , and O 3 (Maahs, 1983) or photochemical oxidation of SO 2 (Yu et al, 2017;Xie et al, 2015), catalytic oxidation of SO 2 by transition metal ions (TMI) (Warneck, 2018;Martin and Good, 1991;Wang et al, 2021) and oxidation of SO 2 by NO 2 (He et al, 2014;Clifton et al, 1988;Wang et al, 2016;Cheng et al, 2016;Wu et al, 2019;Spindler et al, 2003) in aqueous phase and heterogeneous oxidation of SO 2 on black carbon (Zhao et al, 2017;Zhang et al, 2020;Yao et al, 2020), have been proposed based on field measurements and laboratory and modeling studies. However, the relative contribution of these pathways to the SO 2− 4 production is still controversial.…”

Section: Introductionmentioning

confidence: 99%

Ammonium nitrate promotes sulfate formation through uptake kinetic regime

et al. 2021

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Abstract. Although the anthropogenic emissions of SO2 have decreased significantly in China, the decrease in SO42- in PM2.5 is much smaller than that of SO2. This implies an enhanced formation rate of SO42- in the ambient air, and the mechanism is still under debate. This work investigated the formation mechanism of particulate sulfate based on statistical analysis of long-term observations in Shijiazhuang and Beijing supported with flow tube experiments. Our main finding was that the sulfur oxidation ratio (SOR) was exponentially correlated with ambient RH in Shijiazhuang (SOR = 0.15+0.0032×exp⁡(RH/16.2)) and Beijing (SOR = -0.045+0.12×exp⁡(RH/37.8)). In Shijiazhuang, the SOR is linearly correlated with the ratio of aerosol water content (AWC) in PM2.5 (SOR = 0.15+0.40×AWC/PM2.5). Our results suggest that uptake of SO2 instead of oxidation of S(IV) in the particle phase is the rate-determining step for sulfate formation. NH4NO3 plays an important role in the AWC and the change of particle state, which is a crucial factor determining the uptake kinetics of SO2 and the enhanced SOR during haze days. Our results show that NH3 significantly promoted the uptake of SO2 and subsequently the SOR, while NO2 had little influence on SO2 uptake and SOR in the presence of NH3.

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Sulfate formation is dominated by manganese-catalyzed oxidation of SO2 on aerosol surfaces during haze events

Cited by 172 publications

References 73 publications

Aqueous-phase reactive species formed by fine particulate matter from remote forests and polluted urban air

Aqueous-phase reactive species formed by fine particulate matter from remote forests and polluted urban air

Influence of organic aerosol composition determined by offline FIGAERO-CIMS on particle absorptive properties in autumn Beijing

Ammonium nitrate promotes sulfate formation through uptake kinetic regime

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