On the importance of atmospheric loss of organic nitrates by aqueous-phase ·OH-oxidation

González-Sánchez, Juan Miguel; Brun, Nicolas; Wu, Junteng; Morin, Julien; Temime-Rousell, Brice; Ravier, Sylvain; Mouchel‐Vallon, Camille; Clément, Jean‐Louis; Monod, Anne

doi:10.5194/acp-2020-684

Cited by 2 publications

(7 citation statements)

References 35 publications

(54 reference statements)

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“…All the performed photolysis experiments, including experimental conditions, and kinetic results are appended in Table S3. As shown in our previous study (González-Sánchez et al, 2021), isopropyl nitrates and isobutyl nitrate are subject to significant evaporation to the reactor's headspace, and α-nitrooxyacetone is subject to hydrolysis. Therefore, control experiments (under dark conditions) were performed to subtract the evaporation and/or hydrolysis kinetic contributions (see Table S4).…”

Section: Experimental Protocol and Determination Of Experimental Rono...mentioning

confidence: 57%

“…Furthermore, slight quantities of •OH radicals were formed during the photolysis experiments (via photolysis of the produced HNO2 and NO2 -). Since •OH radicals react with RONO2 (González-Sánchez et al, 2021), their attack was considered (Eq. ( 1)) to precisely determine the RONO2 aqueous-phase photolysis rate constant.…”

Section: Experimental Protocol and Determination Of Experimental Rono...mentioning

confidence: 99%

“…In the same manner as in González-Sánchez et al, (2021), the partitioning between the gas and aqueous phase was investigated under two different scenarios: i) under cloud/fog conditions (LWC = 0.35 g m -3 ), and ii) under wet aerosol conditions (LWC = 3 •10 -5 g m -3 ). The partitioning of each molecule in the aqueous phase was calculated using Eq.…”

Section: Photochemical Sink Contributions To Rono2 Multiphase Lifetimesmentioning

confidence: 99%

“…Experimental values were used for 𝑘 𝑂𝐻,𝑎𝑞 and 𝑘 𝑂𝐻,𝑔𝑎𝑠 when available or they were calculated using the group contribution methods presented in González-Sánchez et al, (2021) and Jenkin et al, (2018), respectively. 𝐽 𝑎𝑞 and 𝐽 𝑔𝑎𝑠 were calculated as described in Section 3 when experimental aqueous or gas-phase absorption cross-sections were available.…”

Section: Photochemical Sink Contributions To Rono2 Multiphase Lifetimesmentioning

confidence: 99%

“…However, only a small fraction (between 9 % and 34 % for α-and β-pinene RONO2) of the total pool of organic nitrates undergoes hydrolysis (Takeuchi and Ng, 2019;Wang et al, 2021). Aqueous-phase •OH-oxidation has been reported to be an important sink for non-volatile terpene RONO2, even though the •OH attack is more effectively hindered in the aqueous phase than in the gas phase (González-Sánchez et al, 2021). Nevertheless, limited information is available for RONO2 aqueousphase photolysis.…”

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confidence: 99%

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On the importance of multiphase photolysis of organic nitrates on their global atmospheric removal

González-Sánchez

Brun

et al. 2023

Preprint

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Abstract. Organic nitrates (RONO2) are secondary compounds, and their fate is related to the transport and removal of NOx in the atmosphere. While previous research studies have focused on the reactivity of these molecules in the gas phase, their reactivity in condensed phases remains poorly explored despite their ubiquitous presence in submicron aerosol. This work investigated for the first time the aqueous-phase photolysis rate constants and quantum yields of four RONO2 (isopropyl nitrate, isobutyl nitrate, α-nitrooxyacetone, and 1-nitrooxy-2-propanol). Our results showed much lower photolysis rate constants for these RONO2 in the aqueous phase than in the gas phase. From alkyl nitrates to polyfunctional RONO2, no significant increase of their aqueous-phase photolysis rate constants was observed, even for RONO2 with conjugated carbonyl groups, in contrast with the corresponding gas-phase photolysis reactions. Using these new results, extrapolated to other alkyl and polyfunctional RONO2, as well as other atmospheric sinks (hydrolysis, gas phase photolysis, aqueous and gas phase ·OH oxidation, dry and wet deposition) multiphase atmospheric lifetimes were calculated for 45 atmospherically relevant RONO2 along with the relative importance of each sink. Their lifetimes range from a few minutes to several hours depending on the RONO2 chemical structure and its water solubility. In general, multiphase atmospheric lifetimes are lengthened when RONO2 partition to the aqueous phase, especially for conjugated carbonyl nitrates for which lifetimes can increase up to 100 %. Furthermore, our results show that aqueous-phase ·OH oxidation is a major sink for water-soluble RONO2 (KH > 105 M atm–1) ranging from 50 to 70 % of their total sink at high LWC (0.35 g m–3). These results highlight the importance of investigating the aqueous-phase RONO2 reactivity to understand how it affects their ability to transport air pollution.

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Section: Experimental Protocol and Determination Of Experimental Rono...mentioning

confidence: 57%

Section: Experimental Protocol and Determination Of Experimental Rono...mentioning

confidence: 99%

Section: Photochemical Sink Contributions To Rono2 Multiphase Lifetimesmentioning

confidence: 99%

Section: Photochemical Sink Contributions To Rono2 Multiphase Lifetimesmentioning

confidence: 99%

mentioning

confidence: 99%

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On the importance of multiphase photolysis of organic nitrates on their global atmospheric removal

González-Sánchez

Brun

et al. 2023

Preprint

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Formation of Inorganic Sulfate and Volatile Nonsulfated Products from Heterogeneous Hydroxyl Radical Oxidation of 2-Methyltetrol Sulfate Aerosols: Mechanisms and Atmospheric Implications

Xu,

Chen,

et al. 2024

Environ. Sci. Technol. Lett.

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Chemical transformation of 2-methyltetrol sulfates (2-MTS), key isoprene-derived secondary organic aerosol (SOA) constituents, through heterogeneous hydroxyl radical (•OH) oxidation can result in the formation of previously unidentified atmospheric organosulfates (OSs). However, detected OSs cannot fully account for the sulfur content released from reacted 2-MTS, indicating the existence of sulfur in forms other than OSs such as inorganic sulfates. This work investigated the formation of inorganic sulfates through heterogeneous •OH oxidation of 2-MTS aerosols. Remarkably, high yields of inorganic sulfates, defined as the moles of inorganic sulfates produced per mole of reacted 2-MTS, were observed in the range from 0.48 ± 0.07 to 0.68 ± 0.07. These could be explained by the production of sulfate (SO4 •–) and sulfite (SO3 •–) radicals through the cleavage of C–O(S) and (C)O–S bonds, followed by aerosol-phase reactions. Additionally, nonsulfated products resulting from bond cleavage were likely volatile and evaporated into the gas phase, as evidenced by the observed aerosol mass loss (≤25%) and concurrent size reduction upon oxidation. This investigation highlights the significant transformation of sulfur from its organic to inorganic forms during the heterogeneous oxidation of 2-MTS aerosols, potentially influencing the physicochemical properties and environmental impacts of isoprene-derived SOAs.

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On the importance of atmospheric loss of organic nitrates by aqueous-phase ·OH-oxidation

Cited by 2 publications

References 35 publications

On the importance of multiphase photolysis of organic nitrates on their global atmospheric removal

On the importance of multiphase photolysis of organic nitrates on their global atmospheric removal

Formation of Inorganic Sulfate and Volatile Nonsulfated Products from Heterogeneous Hydroxyl Radical Oxidation of 2-Methyltetrol Sulfate Aerosols: Mechanisms and Atmospheric Implications

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