Organosulfate Formation through the Heterogeneous Reaction of Sulfur Dioxide with Unsaturated Fatty Acids and Long‐Chain Alkenes

Passananti, Monica; Kong, Lingdong; Shang, Jing; Dupart, Y.; Perrier, S.; Chen, Jianmin; Donaldson, D. J.; George, Christian

doi:10.1002/anie.201605266

Cited by 73 publications

(91 citation statements)

References 11 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Several recent studies have revealed the formation of OSs from photooxidation of anthropogenic precursors, such as polycyclic aromatic hydrocarbons (Riva et al, 2015) or long‐chain alkanes (Riva, Barbosa, et al, 2016), on sulfate seed particles. Moreover, direct formation of OSs from uptake of gaseous SO 2 by unsaturated fatty acids (Passananti et al, 2016; Shang et al, 2016) and organic peroxides (Wang, Zhou, et al, 2019) and OS formation from reaction of hydrogen sulfite with unsaturated carbonyl compounds in the presence of Fe 3+ (Huang, Cochran, et al, 2018) have been reported. However, the atmospheric relevance of these processes has yet to be elucidated.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2020

Self Cite

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: Introductionmentioning

confidence: 99%

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

et al. 2020

Self Cite

View full text Add to dashboard Cite

show abstract

“…Several laboratory studies focussed on OS formation mechanisms from a variety of biogenic as well as anthropogenic volatile organic compounds, which include isoprene (Riva et al 2016b;Schindelka et al 2013;Surratt et al 2010), monoterpenes (MTs, Iinuma et al 2007aIinuma et al , 2007bSurratt et al 2008), pinonaldehyde (Liggio and Li 2006), sesquiterpenes (SQTs, Chan et al 2011), unsaturated aldehydes (Shalamzari et al 2016), and polycyclic aromatic hydrocarbons as well as alkanes (Riva et al 2016a). Moreover, direct formation of OSs from reactions of gaseous SO 2 with fatty acids (Passananti et al 2016) and limonene-derived Criegee intermediates were reported (Ye et al 2018). In addition to aerosol acidity, liquid water content (LWC) was shown to play a key role in OS formation, as demonstrated by studies on the aqueous-phase and heterogeneous OS formation mechanisms (McNeill 2015;McNeill et al 2012).…”

Section: Introductionmentioning

confidence: 99%

Quantification of known and unknown terpenoid organosulfates in PM10 using untargeted LC–HRMS/MS: contrasting summertime rural Germany and the North China Plain

et al. 2019

View full text Add to dashboard Cite

Environmental context. Secondary organic aerosols account for a major fraction of atmospheric particulate matter, affecting both climate and human health. Organosulfates, abundant compounds in organic aerosols, are difficult to measure because of the lack of authentic standards. Here we quantify terpene-derived organosulfates in atmospheric particulate matter at a rural site in Germany and at the North China Plain using a combined target/non-target high-resolution mass spectrometry approach.Abstract. Organosulfates (OSs) are a ubiquitous class of compounds in atmospheric aerosol particles. However, a detailed quantification of OSs is commonly hampered because of missing authentic standards and the abundance of unknown OSs. Using a combined targeted and untargeted approach of high-resolution liquid chromatography-Orbitrap mass spectrometry (LC-Orbitrap MS), we quantified for the first time the total concentrations of known and unknown monoterpene (MT) and sesquiterpene (SQT) OSs in summertime PM 10 particulate matter from field studies in rural Germany (MEL) and the North China Plain (NCP). At each site, we observed more than 50 MT-OSs, 13 of which were detectable at both sites. For both locations, median concentrations of MT-OSs were in the range of 10 to 40 ng m À3 , to which the 13 common MT-OSs contributed on average .50 %. The main contributor to MT-OSs was C 9 H 16 O 7 S (MT-OS 267) with average mass concentrations of 2.23 and 6.38 ng m À3 for MEL and NCP respectively. The concentrations of MT-OSs correlated with the concentrations of MT oxidation products only for MEL. For NCP, the low concentrations of MT oxidation products (i.e. typically ,1 ng m À3 ) suggested a suppression of carboxylic acid formation under high concentrations of NO x and particulate sulfate. Furthermore, we observed 17 SQT-OSs for the MEL samples, whereas 40 SQT-OSs were detected in the NCP samples. Only five of these SQT-OSs were detectable at both sites. Correspondingly, the total concentrations of SQT-OSs were larger for NCP than for MEL, which suggested large differences in the particle chemistry. In particular, aerosol acidity was found to be a key factor during SQT-OS formation, and was probably not sufficient in the PM 10 from MEL.

show abstract

“…In order to assess and quantify the role of the heterogeneous reactions of SO 2 in sulfate formation, laboratory studies are needed to understand the reaction process and obtain kinetic parameters for modeling, such as uptake coefficients of SO 2 . Among many studies investigating the heterogeneous reactions of SO 2 on various particles (Goodman et al, 2001;Li et al, 2011Li et al, , 2004Li et al, , 2006Shang et al, 2010;Huang et al, , 2016Zhou et al, 2014;Kong et al, 2014;Passananti et al, 2016;Cui et al, 2008;Chu et al, 2016;Zhao et al, 2015;Wu et al, 2011He et al, 2014Liu et al, 2012;Ma et al, 2008;Park and Jang, 2016;Ullerstam et al, 2002Ullerstam et al, , 2003Sorimachi et al, 2001), only a few have investigated the heterogeneous reaction of SO 2 in the presence of NO 2 (He et al, 2014;Liu et al, 2012;Ma et al, 2008Ma et al, , 2017Park and Jang, 2016;Ullerstam et al, 2003). These studies found that NO 2 can promote sulfate formation from SO 2 oxidation (He et al, 2014;Liu et al, 2012;Ma et al, 2008;Park and Jang, 2016;Ullerstam et al, 2003).…”

Section: Introductionmentioning

confidence: 99%

Multiphase oxidation of SO2 by NO2 on CaCO3 particles

et al. 2018

Self Cite

View full text Add to dashboard Cite

Abstract. Heterogeneous/multiphase oxidation of SO2 by NO2 on solid or aqueous particles is thought to be a potentially important source of sulfate in the atmosphere, for example, during heavily polluted episodes (haze), but the reaction mechanism and rate are uncertain. In this study, in order to assess the importance of the direct oxidation of SO2 by NO2 we investigated the heterogeneous/multiphase reaction of SO2 with NO2 on individual CaCO3 particles in N2 using Micro-Raman spectroscopy. In the SO2 ∕ NO2 ∕ H2O ∕ N2 gas mixture, the CaCO3 solid particle was first converted to the Ca(NO3)2 droplet by the reaction with NO2 and the deliquescence of Ca(NO3)2, and then NO2 oxidized SO2 in the Ca(NO3)2 droplet forming CaSO4, which appeared as needle-shaped crystals. Sulfate was mainly formed after the complete conversion of CaCO3 to Ca(NO3)2, that is, during the multiphase oxidation of SO2 by NO2. The precipitation of CaSO4 from the droplet solution promoted sulfate formation. The reactive uptake coefficient of SO2 for sulfate formation is on the order of 10−8, and RH enhanced the uptake coefficient. We estimate that the direct multiphase oxidation of SO2 by NO2 is not an important source of sulfate in the ambient atmosphere compared with the SO2 oxidation by OH in the gas phase and is not as important as other aqueous-phase pathways, such as the reactions of SO2 with H2O2, O3, and O2, with or without transition metals.

show abstract

Organosulfate Formation through the Heterogeneous Reaction of Sulfur Dioxide with Unsaturated Fatty Acids and Long‐Chain Alkenes

Cited by 73 publications

References 11 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

Quantification of known and unknown terpenoid organosulfates in PM10 using untargeted LC–HRMS/MS: contrasting summertime rural Germany and the North China Plain

Multiphase oxidation of SO<sub>2</sub> by NO<sub>2</sub> on CaCO<sub>3</sub> particles

Contact Info

Product

Resources

About

Organosulfate Formation through the Heterogeneous Reaction of Sulfur Dioxide with Unsaturated Fatty Acids and Long‐Chain Alkenes

Cited by 73 publications

References 11 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

Quantification of known and unknown terpenoid organosulfates in PM10 using untargeted LC–HRMS/MS: contrasting summertime rural Germany and the North China Plain

Multiphase oxidation of SO&lt;sub&gt;2&lt;/sub&gt; by NO&lt;sub&gt;2&lt;/sub&gt; on CaCO&lt;sub&gt;3&lt;/sub&gt; particles

Contact Info

Product

Resources

About

Multiphase oxidation of SO<sub>2</sub> by NO<sub>2</sub> on CaCO<sub>3</sub> particles