the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
SOA yields from C10 alkanes and oxygenates and their relation to highly oxygenated organic molecules (HOM)
Abstract. Alkanes are hydrocarbons that are emitted to the atmosphere mainly by human activities such as combustion processes and via the use of volatile chemical products (VCPs). They are an important group of volatile organic compounds (VOCs) that can produce secondary organic aerosol (SOA) in the atmosphere via hydroxyl (OH) radical initiated reactions. For many other compound groups (e.g., aromatics and monoterpenes), highly oxygenated organic molecules (HOMs) formed via autoxidation have been shown to be an important link between VOCs and SOA. Although alkane SOA has been intensively studied over the last decades, the importance of autoxidation and HOM in this system has received limited attention. The first HOM observations were only recently reported, but their relation so SOA has not been directly studied. Here, we show results of SOA yields from seven C10 alkanes and their oxygenated derivatives in oxidation flow reactor experiments. We observe the well-known behaviour of increased SOA yield with different structure in the order of cyclic > linear > branched. We also measured HOMs, and all seven SOA precursors produced detectable amounts of products, but HOM quantification was not possible due to the experimental setup configuration focusing on SOA formation. However, a comparison to previously reported HOM yields for the same precursors was conducted, showing an overall correlation between HOM and SOA yields. Although not quantifiable, our own HOM observations did indicate that multi-generation OH oxidation played an important role in the SOA formation in our study.
- Preprint
(1182 KB) - Metadata XML
- BibTeX
- EndNote
Status: open (until 28 Apr 2025)
-
RC1: 'Comment on egusphere-2025-910', Anonymous Referee #1, 11 Apr 2025
reply
- In this paper, the SOA was produced from the photooxidation of various alkanes in the absence of NOx. As authors described, alkanes are a major part of anthropogenic VOC emissions. This means that the atmospheric oxidation of alkanes is more liked processed in the presence of NOx. In particular, urban air environments are typically in the high NOx region. Authors need to discuss about the potential impact of NOx on HOM productions and alkanes SOA yields.
- Lines 75-80. Is there a specific reason why RH was set to 22%.
- Line 89-92. Please describe the difference between the measured and modelled OH exposure more quantitatively. In a typical experiment, how big of a difference would this be in calculated precursor consumption values?
- Line 113-115. Were wall losses to the PAM and/or tubing corrected for? If not, how can the measured SOA mass concentrations, and thus yields, be trusted if HOM condensation to the wall is a significant issue? Is it possible to lower the oxidant concentrations in the PAM and reduce the number of instruments used at a time in order to reduce HOM yield and sample flow to improve the HOM measurements? If HOMs would be significantly lost regardless of sample flow, how can any particle mass measurements be trusted?
- Lines 148-155 on page 6 and page 7. Please explain why cycloalkanes had the highest SOA yields.
- Line 151 on page 7. Authors mentioned that SOA mass concentration were at atmospherically relevant levels (< 20 µg/m3) for all precursors. All experiments were under controlled environments and not relevance to atmospheric conditions. The description about SOA mass concentrations is not appropriate.
- Lines 174-179. Please clarify the seed types and their role on SOA yields. In the absence of inorganic seed, SOA formation can be retarded but its yield is not affected. The organic seed aerosol can increase SOA yields.
- Line 201-206. Authors need better explanation on why this study is not expected to be in the range of ambient SOA studies. Even if they include some biogenic SOA with lower H/C ratios, wouldn’t that only lower the bottom of the range without having an impact on the upper limit of the range? What were the oxidation conditions (i.e NOx and oxidant concentration) of the vehicle exhaust studies? Are they comparable with this study?
- Figure 3. Again, environmental conditions of alkane SOA formation of this study is very different from ambient air. Authors need to explain why alkane SOA of this study is comparable with SOA in ambient air.
- Figure 4. Overall, mechanistic explanations for different HOM yields are weak. For example, among oxygenated VOC, why did different VOCs yield different HOM productions?
- Figure 5. The reviewer cannot understand the role of Figure 5 to explain the formation of HOMs. Naturally, higher concentrations of precursor with a given concentration of oxidants will produce less oxidized products and vice versa.
- Line 227-231. HOMs are discussed in the introduction in relation to autoxidation (line 46). Typically, the RO radical that initiates the alkane autoxidation process is formed in the reaction with NO. Discuss the significance of the RO2 + RO2 reaction in no NOx conditions.
- Line 231-235. It would be beneficial to the reader to provide a mechanism where oxidation is initiated and proceeds through the major reactions that are expected to occur under these conditions which ultimately lead to HOM (>6 Oxygen atoms) identified in Figs. A2-A8.
- What is the impact of heterogeneous chemistry on SOA yields?
- Appendix A. There is a dilution flow (10 LPM). What is the impact of dilution of air stream on SOA production? Some SOA products can be off-gassing from the aerosol. Please clarify this issue.
- Figures A2-A8. What is the signal to noise (S/N) ratio? In general, the signal should be 3 times higher than the noise. Were elemental compositions marked on Figures statistically significant.
Citation: https://doi.org/10.5194/egusphere-2025-910-RC1 -
RC2: 'Comment on egusphere-2025-910', Anonymous Referee #2, 16 Apr 2025
reply
Please find my detailed review report in the attached pdf.
Viewed
HTML | XML | Total | BibTeX | EndNote | |
---|---|---|---|---|---|
129 | 31 | 8 | 168 | 4 | 3 |
- HTML: 129
- PDF: 31
- XML: 8
- Total: 168
- BibTeX: 4
- EndNote: 3
Viewed (geographical distribution)
Country | # | Views | % |
---|---|---|---|
United States of America | 1 | 55 | 38 |
China | 2 | 20 | 13 |
Finland | 3 | 20 | 13 |
undefined | 4 | 7 | 4 |
Germany | 5 | 5 | 3 |
Total: | 0 |
HTML: | 0 |
PDF: | 0 |
XML: | 0 |
- 1
- 55