the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
| 26 Oct 2022
SO2 enhances aerosol formation from anthropogenic volatile organic compound ozonolysis by producing sulfur-containing compounds
Abstract. Sulfur dioxide (SO2) can affect aerosol formation in the atmosphere, but the underlying mechanisms remain unclear. Here, we investigate aerosol formation and composition from the ozonolysis of cyclooctene with and without SO2 addition in a smog chamber. Liquid chromatography equipped with high-resolution tandem mass spectrometry measurements indicate that monomer carboxylic acids and corresponding dimers with acid anhydride and aldol structures are important components in particles formed in the absence of SO2. A 9.4–12.6 time increase in particle maximum number concentration is observed in the presence of 14–192 ppb SO2. This increase is largely attributed to sulfuric acid (H2SO4) formation from the reactions of stabilized Criegee intermediates with SO2. In addition, a number of organosulfates (OSs) are detected in the presence of SO2, which are likely products formed from the heterogeneous reactions of oxygenated species with H2SO4. The molecular structures of OSs are also identified based on tandem mass spectrometry analysis. It should be noted that some of these OSs have been found in previous field studies but were classified as compounds from unknown sources or of unknown structures. The observed OSs are less volatile than their precursors and therefore are more effective contributors to particle formation and growth, partially leading to the increase in particle volume concentration under SO2-presence conditions. Our results provide an in-depth molecular-level insight into how SO2 alters particle formation and composition.
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The requested preprint has a corresponding peer-reviewed final revised paper. You are encouraged to refer to the final revised version.
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Journal article(s) based on this preprint
Interactive discussion
Status: closed
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RC1: 'Comment on egusphere-2022-1068', Anonymous Referee #1, 31 Oct 2022
The manuscript by Yang et al. describes a set of laboratory measurements, in which they investigated SO2 effects on the formation and chemical composition of particles from anthropogenic volatile organic compound ozonolysis. Various monomeric and dimeric products with C, H, and O atoms were observed under SO2-free conditions. The authors found that SO2 presence can induce the formation of sulfur-containing compounds. They suggested that the observed sulfur-containing compounds have stronger ability for particle formation than corresponding precursors, leading to an enhancement of particle formation. Structures and reasonable formation mechanisms of these sulfur-containing compounds were also proposed. Overall, the experimental design, results, and discussion of this manuscript are presented in a logical sequence that is easy to follow and understand. The paper provides new and valuable results for our understanding of the details of SO2 roles in aerosol formation, and also guidance and inspiration for the community that reads ACP. Therefore, I would recommend the publication of this work if the author consider the minor comments below.
Specific comments:
- The authors did a great job of explaining the reasons why their study would be of importance and interest. However, there is just brief text regarding the influences of SO2 on aerosol chemistry. Some recent literatures should be considered.
- Deng, P. S. J. Lakey, Y. Wang, P. Li, J. Xu, H. Pang, J. Liu, X. Xu, X. Li, X. Wang, Y. Zhang, M. Shiraiwa and S. Gligorovski, Daytime SO2 chemistry on ubiquitous urban surfaces as a source of organic sulfur compounds in ambient air, Sci. Adv., 2022, 8, eabq6830.
- Wang, T. Liu, J. Jang, J. P. D. Abbatt and A. W. H. Chan, Heterogeneous interactions between SO2 and organic peroxides in submicron aerosol, Atmos. Chem. Phys., 2021, 21, 6647-6661.
- P4, L92. The authors mentioned that cyclohexane was injected into the chamber to scavenge OH radical. It is also worth mentioning how did the authors determine that OH had been successfully scavenged.
- P5, L118 and L128. Particle production experiments were carried out as batch mode experiments. Therefore, the chemical reaction systems were evolving during the ozonolysis of anthropogenic volatile compound. During which reaction period of the experiments did the authors collect aerosol particles? Please indicate this information.
- P6, L130. It should be also stated clear how the extraction was done (i.e., whole filter or punches? device?)
- P7, L162–167. Perhaps it is better for the understanding of readers to include some relevant citations.
- P7, L168. Full equation from Li et al. (2016) should be given.
- P9, L225. From Fig. S2, the volume concentration of aerosol particles reached its maximum within 240 min. So, what is the definition of the initial stage of particle production experiment?
- The authors mentioned that the enhancement of aerosol particles was mainly due to the formation of inorganic and organic sulfates. Although wall losses of organic vapors may be negligible as the author discussed, previous studies suggest that increased particle surface area by SO2 may cause the increase in particle volume concentration. Would this be a possible clarification?
- P17, L378. Could you provide some more details about the IR absorption of different functional groups? Perhaps in the Supplement?
- P19, L 396. The Reviewer would recommend the author to present briefly the strengths of ESI-MS in characterizing organosulfate. This may be significant in supporting the production of organosulfate.
- P22, Figure 7. The legend “Precursor” is confusing since cyclooctene is also referred to as a precursor in this manuscript. Suggest different legend such as organosulfate precursor or something else.
Citation: https://doi.org/10.5194/egusphere-2022-1068-RC1 -
AC1: 'Reply on RC1', Lin Du, 07 Dec 2022
The comment was uploaded in the form of a supplement: https://egusphere.copernicus.org/preprints/2022/egusphere-2022-1068/egusphere-2022-1068-AC1-supplement.pdf
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AC3: 'Reply on RC1', Lin Du, 09 Dec 2022
The comment was uploaded in the form of a supplement: https://egusphere.copernicus.org/preprints/2022/egusphere-2022-1068/egusphere-2022-1068-AC3-supplement.pdf
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RC2: 'Review of egusphere-2022-1068', Anonymous Referee #2, 22 Nov 2022
General comments:
This paper describes the enhancement of aerosol formation in the presence of SO2 during cyclooctene ozonolysis. The composition of the formed SOA was investigated by means of ATR-FTIR and LC-MS/MS and the authors found that the enhancement was largely attributed to the formation of H2SO4 and organosulfates (OSs). By using high-resolution MS/MS, the molecular structures of many OSs were proposed in this work. I think that this study was well-conducted and that the data presented here are valuable for the understanding of the SOA formation. In addition, the paper is generally well-written. I recommend this paper to be published in Atmospheric Chemistry and Physics after the authors’ consideration of my minor comments detailed below.
Specific comments:
- Page 4, Section 2.1: It is better to show the rate constant for the reaction of cyclooctene with O3.
- Page 5, Table 1: There is no information about the reaction time. Is it 300 min? I guess that the reaction of cyclooctene with O3 was completed within several minutes. Why did the authors measure for such the long reaction time?
- Page 17, Lines 383â387: In Hawkins et al (2010), an absorption band at 876 cmâ1 was mentioned for organosulfates. There is no mention about an absorption band of organosulfates in Coury and Dillner (2008). How did the authors attribute absorption bands at 1413 and 1095 cmâ1 to organosulfates? Is there any additional evidence?
- Page 21, Figure 6: In this figure, the formation of many kinds of compounds having hydroxy groups is proposed. Actually, many of ion signals obtained by LC-MS/MS were assigned to compounds having hydroxy groups. But it seems that the peak of alcohol-COH in the ATR-FTIR (3500â3200 cmâ1) is quite smaller than that of carbonyl at 1702 cmâ1. Is it reasonable?
- Page 22, Figure 7: I think that the calculation of DBE (eqn. (1)) cannot be applied to organosulfates. I think that the DBE of precursors of OSs is meaningful.
Citation: https://doi.org/10.5194/egusphere-2022-1068-RC2 -
AC2: 'Reply on RC2', Lin Du, 07 Dec 2022
The comment was uploaded in the form of a supplement: https://egusphere.copernicus.org/preprints/2022/egusphere-2022-1068/egusphere-2022-1068-AC2-supplement.pdf
Interactive discussion
Status: closed
-
RC1: 'Comment on egusphere-2022-1068', Anonymous Referee #1, 31 Oct 2022
The manuscript by Yang et al. describes a set of laboratory measurements, in which they investigated SO2 effects on the formation and chemical composition of particles from anthropogenic volatile organic compound ozonolysis. Various monomeric and dimeric products with C, H, and O atoms were observed under SO2-free conditions. The authors found that SO2 presence can induce the formation of sulfur-containing compounds. They suggested that the observed sulfur-containing compounds have stronger ability for particle formation than corresponding precursors, leading to an enhancement of particle formation. Structures and reasonable formation mechanisms of these sulfur-containing compounds were also proposed. Overall, the experimental design, results, and discussion of this manuscript are presented in a logical sequence that is easy to follow and understand. The paper provides new and valuable results for our understanding of the details of SO2 roles in aerosol formation, and also guidance and inspiration for the community that reads ACP. Therefore, I would recommend the publication of this work if the author consider the minor comments below.
Specific comments:
- The authors did a great job of explaining the reasons why their study would be of importance and interest. However, there is just brief text regarding the influences of SO2 on aerosol chemistry. Some recent literatures should be considered.
- Deng, P. S. J. Lakey, Y. Wang, P. Li, J. Xu, H. Pang, J. Liu, X. Xu, X. Li, X. Wang, Y. Zhang, M. Shiraiwa and S. Gligorovski, Daytime SO2 chemistry on ubiquitous urban surfaces as a source of organic sulfur compounds in ambient air, Sci. Adv., 2022, 8, eabq6830.
- Wang, T. Liu, J. Jang, J. P. D. Abbatt and A. W. H. Chan, Heterogeneous interactions between SO2 and organic peroxides in submicron aerosol, Atmos. Chem. Phys., 2021, 21, 6647-6661.
- P4, L92. The authors mentioned that cyclohexane was injected into the chamber to scavenge OH radical. It is also worth mentioning how did the authors determine that OH had been successfully scavenged.
- P5, L118 and L128. Particle production experiments were carried out as batch mode experiments. Therefore, the chemical reaction systems were evolving during the ozonolysis of anthropogenic volatile compound. During which reaction period of the experiments did the authors collect aerosol particles? Please indicate this information.
- P6, L130. It should be also stated clear how the extraction was done (i.e., whole filter or punches? device?)
- P7, L162–167. Perhaps it is better for the understanding of readers to include some relevant citations.
- P7, L168. Full equation from Li et al. (2016) should be given.
- P9, L225. From Fig. S2, the volume concentration of aerosol particles reached its maximum within 240 min. So, what is the definition of the initial stage of particle production experiment?
- The authors mentioned that the enhancement of aerosol particles was mainly due to the formation of inorganic and organic sulfates. Although wall losses of organic vapors may be negligible as the author discussed, previous studies suggest that increased particle surface area by SO2 may cause the increase in particle volume concentration. Would this be a possible clarification?
- P17, L378. Could you provide some more details about the IR absorption of different functional groups? Perhaps in the Supplement?
- P19, L 396. The Reviewer would recommend the author to present briefly the strengths of ESI-MS in characterizing organosulfate. This may be significant in supporting the production of organosulfate.
- P22, Figure 7. The legend “Precursor” is confusing since cyclooctene is also referred to as a precursor in this manuscript. Suggest different legend such as organosulfate precursor or something else.
Citation: https://doi.org/10.5194/egusphere-2022-1068-RC1 -
AC1: 'Reply on RC1', Lin Du, 07 Dec 2022
The comment was uploaded in the form of a supplement: https://egusphere.copernicus.org/preprints/2022/egusphere-2022-1068/egusphere-2022-1068-AC1-supplement.pdf
-
AC3: 'Reply on RC1', Lin Du, 09 Dec 2022
The comment was uploaded in the form of a supplement: https://egusphere.copernicus.org/preprints/2022/egusphere-2022-1068/egusphere-2022-1068-AC3-supplement.pdf
-
RC2: 'Review of egusphere-2022-1068', Anonymous Referee #2, 22 Nov 2022
General comments:
This paper describes the enhancement of aerosol formation in the presence of SO2 during cyclooctene ozonolysis. The composition of the formed SOA was investigated by means of ATR-FTIR and LC-MS/MS and the authors found that the enhancement was largely attributed to the formation of H2SO4 and organosulfates (OSs). By using high-resolution MS/MS, the molecular structures of many OSs were proposed in this work. I think that this study was well-conducted and that the data presented here are valuable for the understanding of the SOA formation. In addition, the paper is generally well-written. I recommend this paper to be published in Atmospheric Chemistry and Physics after the authors’ consideration of my minor comments detailed below.
Specific comments:
- Page 4, Section 2.1: It is better to show the rate constant for the reaction of cyclooctene with O3.
- Page 5, Table 1: There is no information about the reaction time. Is it 300 min? I guess that the reaction of cyclooctene with O3 was completed within several minutes. Why did the authors measure for such the long reaction time?
- Page 17, Lines 383â387: In Hawkins et al (2010), an absorption band at 876 cmâ1 was mentioned for organosulfates. There is no mention about an absorption band of organosulfates in Coury and Dillner (2008). How did the authors attribute absorption bands at 1413 and 1095 cmâ1 to organosulfates? Is there any additional evidence?
- Page 21, Figure 6: In this figure, the formation of many kinds of compounds having hydroxy groups is proposed. Actually, many of ion signals obtained by LC-MS/MS were assigned to compounds having hydroxy groups. But it seems that the peak of alcohol-COH in the ATR-FTIR (3500â3200 cmâ1) is quite smaller than that of carbonyl at 1702 cmâ1. Is it reasonable?
- Page 22, Figure 7: I think that the calculation of DBE (eqn. (1)) cannot be applied to organosulfates. I think that the DBE of precursors of OSs is meaningful.
Citation: https://doi.org/10.5194/egusphere-2022-1068-RC2 -
AC2: 'Reply on RC2', Lin Du, 07 Dec 2022
The comment was uploaded in the form of a supplement: https://egusphere.copernicus.org/preprints/2022/egusphere-2022-1068/egusphere-2022-1068-AC2-supplement.pdf
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Zhaomin Yang
Narcisse T. Tsona
Xin Luo
The requested preprint has a corresponding peer-reviewed final revised paper. You are encouraged to refer to the final revised version.
- Preprint
(1632 KB) - Metadata XML
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Supplement
(1714 KB) - BibTeX
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- Final revised paper