the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
Molecular Analysis of Secondary Organic Aerosol and Brown Carbon from the Oxidation of Indole
Feng Jiang
Kyla Siemens
Claudia Linke
Yanxia Li
Yiwei Gong
Thomas Leisner
Alexander Laskin
Harald Saathoff
Abstract. Indole (ind) is a nitrogen-containing heterocyclic volatile organic compound commonly emitted from animal husbandry and from different plants like maize with global emissions of 0.1 Tg y-1. The chemical composition and optical properties of indole secondary organic aerosol (SOA) and brown carbon (BrC) are still not well understood. To address this, environmental chamber experiments were conducted to investigate the oxidation of indole at atmospherically relevant concentrations of selected oxidants (OH radicals and O3) with/without NO2. In the presence of NO2, the SOA yields decreased by more than a factor of two but the mass absorption coefficient at 365 nm (MAC365) of ind-SOA was 4.3 ± 0.4 m2 g-1, which was 5 times higher than that in experiments without NO2. In the presence of NO2, C8H6N2O2 (identified as 3-nitroindole) contributed 76 % to the all organic compounds detected by a chemical ionization mass spectrometer, contributing ~50 % of the light absorption at 365 nm (Abs365). In the absence of NO2, the dominating chromophore was C8H7O3N contributing to 20–30 % of Abs365. Indole contributes substantially to the formation of secondary BrC and its potential impact on the atmospheric radiative transfer is further enhanced in the presence of NO2, as it significantly increases the specific light absorption of ind-SOA by facilitating the formation of 3-nitroindole. This work provides new insights into an important process of brown carbon formation by interaction of two pollutants, NO2 and indole, mainly emitted by anthropogenic activities.
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Feng Jiang et al.
Status: open (until 06 Oct 2023)
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RC1: 'Comment on egusphere-2023-1804', Anonymous Referee #1, 19 Sep 2023
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The manuscript by Jiang et al. investigates the oxidation of indole by selected oxidants (OH radicals and O3) with/without NO2. The authors report the chemical composition and optical properties of indole SOA (ind-SOA) under the investigated conditions. In the presence of NO2, the ind-SOA yields decreased by more than a factor of two, but the mass absorption coefficient at 365 nm of ind-SOA was 5 times higher than that of the SOA form without NO2. The global emission factors of indole could be around half of the emissions of the most abundant amines, trimethylamine. However, there are only limited studies investigating the formation of SOA and BrC from the oxidation of indole. Overall, this study would be a valuable addition to a better understanding of the ind-SOA formation mechanisms and the influence of NO2 on the chemical composition and light-absorbing characteristics of ind-SOA. The results may be particularly important for areas with abundant indole emissions, such as large animal husbandries and maize fields. The manuscript is well-presented, and it could be accepted for publication after considering the comments below.
Line 90: To clarify how the OH concentrations were calculated, the authors could consider adding a few sentences explaining the methodology used.
Lines 95-99 and Figure S2: The O3 was injected into the chamber at around 600-800 ppb in the REF and seed experiments, while in the Seed-NO2 experiment, it was initially added at around 100 ppb and then increased to 600-800 ppb after 30 minutes. The authors may want to provide an explanation for this difference.
Line 100: It would be helpful if the authors could provide more information about the background samples and whether they would react with the reactants.
Line 117: Were the estimated trace gas and particle wall losses corrected?
Lines 132 and 152: Why the methanol and acetonitrile were used to extract the filter samples for different analyses? It would be beneficial if the authors could explain their rationale for selecting these solvents and discuss any potential solvent effects.
FIGAERO-CIMS part: The manuscript does not mention the mass resolution of the instrument used. Additionally, while the authors assumed a uniform sensitivity for different compounds, it is possible that sensitivities vary by order of magnitude. It would be helpful if the authors could provide references from the literature supporting their assumption or consider rephrasing statements regarding “XXX% of CIMS detected compounds.” Furthermore, it would be interesting to know if thermal desorption caused any fragmentation of the compounds and if multimodal thermograms were observed.
Line 172: What would be the reasons for the slightly lower SOA yield in the AS seed experiment than that in the REF experiment? Line 183: What is the seed concentration used in Montoya et al.? Would different seed concentrations play a role in the different yields?
Figure 1b: When calculating the effective density of indole SOA by comparing the AMS and SMPS data, would the seed density affect the results? Was it excluded?
Figure 3: It was mentioned in the figure caption that the Y-axis scale shows the fraction of CxHyOzN1-2 of the total ion intensity, but there are compounds without N atom shown in the Figure.
Line 223: The author attributed the common ions C6H4+ and C5H3+ to be fragmented from 3-nitroindole or C16H12O4N4 (Figure S8), but these ions were also observed in REF and AS experiments.
Figure 4: Please check the caption about the description of the color used in the Figure. For example, “The unassigned chromophores (red)”.
Line 249: 3-nitroindole contributed 76% of compound signals detected by a CIMS, and ~50% of the BrC absorption. Would this indicate there are compounds with low signal intensities that contribute even more than 3-nitroindole to the BrC absorption?
Citation: https://doi.org/10.5194/egusphere-2023-1804-RC1
Feng Jiang et al.
Feng Jiang et al.
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