Competing atmospheric reactions of CH2OO with SO2and water vapour

Berndt, Torsten; Voigtländer, Jens; Stratmann, Frank; Junninen, Heikki; Mauldin, R. L.; Sipilä, Mikko; Kulmala, Markku; Herrmann, Hartmut

doi:10.1039/c4cp02345e

Cited by 99 publications

(149 citation statements)

References 39 publications

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“…Neeb et al (1997) measured rapid reaction of sCI + HCOOH in comparison to sCI + water. However, our results cannot be directly compared to Neeb et al (1997) due to different water reactivity of CH 2 OO (studied by Neeb et al, 1997) and (CH 3 ) 2 COO investigated here (Berndt et al, 2014b). However, our result is very similar to the reaction rate coefficients reported by Welz et al (2012;2104) for reactions of CH 2 OO with SO 2 and HCOOH / CH 3 COOH.…”

Section: Reaction Of Sci With Organic Acidssupporting

confidence: 70%

“…Stone et al (2014) suggest a relatively slow water reaction obtained by a technique similar to the approach by Welz et al (2012), while the older measurements suggest that the water reaction dominates in the atmosphere over "all" other reactions; see for example Hasson et al (2001a). Recent work by Berndt et al (2014b) also suggests that reaction with water (dimer) is relatively fast dominating the atmospheric fate of CH 2 OO. The relative rate coefficients k(loss) / k(sCI + SO 2 ) obtained in this study are close to those obtained by Berndt et al (2012) for sCI from the ozonolysis of trans-2-butene and TME.…”

Section: Sci Yields and Relative Rate Coefficientsmentioning

confidence: 99%

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Reactivity of stabilized Criegee intermediates (sCIs) from isoprene and monoterpene ozonolysis toward SO2 and organic acids

et al. 2014

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Abstract. Oxidation processes in Earth's atmosphere are tightly connected to many environmental and human health issues and are essential drivers for biogeochemistry. Until the recent discovery of the atmospheric relevance of the reaction of stabilized Criegee intermediates (sCIs) with SO 2 , atmospheric oxidation processes were thought to be dominated by a few main oxidants: ozone, hydroxyl radicals (OH), nitrate radicals and, e.g. over oceans, halogen atoms such as chlorine. Here, we report results from laboratory experiments at 293 K and atmospheric pressure focusing on sCI formation from the ozonolysis of isoprene and the most abundant monoterpenes (α-pinene and limonene), and subsequent reactions of the resulting sCIs with SO 2 producing sulfuric acid (H 2 SO 4 ). The measured total sCI yields were (0.15 ± 0.07), (0.27 ± 0.12) and (0.58 ± 0.26) for α-pinene, limonene and isoprene, respectively. The ratio between the rate coefficient for the sCI loss (including thermal decomposition and the reaction with water vapour) and the rate coefficient for the reaction of sCI with SO 2 , k(loss) / k(sCI + SO 2 ), was determined at relative humidities of 10 and 50 %. Observed values represent the average reactivity of all sCIs produced from the individual alkene used in the ozonolysis. For the monoterpene-derived sCIs, the relative rate coefficients k(loss) / k(sCI + SO 2 ) were in the range (2.0-2.4) × 10 12 molecules cm −3 and nearly independent of the relative humidity. This fact points to a minor importance of the sCI + H 2 O reaction in the case of the sCI arising from α-pinene and limonene. For the isoprene sCIs, however, the ratio k(loss) / k(sCI + SO 2 ) was strongly dependent on the relative humidity. To explore whether sCIs could have a more general role in atmospheric oxidation, we investigated as an example the reactivity of acetone oxide (sCI from the ozonolysis of 2,3-dimethyl-2-butene) toward small organic acids, i.e. formic and acetic acid. Acetone oxide was found to react faster with the organic acids than with SO 2 ; k(sCI + acid) / k(sCI + SO 2 ) = (2.8 ± 0.3) for formic acid, and k(sCI + acid) / k(sCI + SO 2 ) = (3.4 ± 0.2) for acetic acid. This finding indicates that sCIs can play a role in the formation and loss of other atmospheric constituents besides SO 2 .

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Section: Reaction Of Sci With Organic Acidssupporting

confidence: 70%

Section: Sci Yields and Relative Rate Coefficientsmentioning

confidence: 99%

Reactivity of stabilized Criegee intermediates (sCIs) from isoprene and monoterpene ozonolysis toward SO2 and organic acids

et al. 2014

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“…Under the experimental conditions in this study, at least for the experiments with low SO 2 concentrations, the oxidation of SO 2 to SO 3 through reaction with the corresponding sCI seems negligible, contrary to the results found for smaller carbonyl oxides (Berndt et al, 2014b). Likewise, the pathway producing ester sulfinic acids (Reaction 5) can be ruled out for 2,5-DHF and 2,3-DHF.…”

Section: Discussioncontrasting

confidence: 49%

Formation of secondary organic aerosols from the ozonolysis of dihydrofurans

et al. 2017

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Abstract. In this work we report the study of the ozonolysis of 2,5-dihydrofuran and 2,3-dihydrofuran and the reaction conditions leading to the formation of secondary organic aerosols. The reactions have been carried out in a Teflon chamber filled with synthetic air mixtures at atmospheric pressure and room temperature. The ozonolysis only produced particles in the presence of SO 2 . Rising relative humidity from 0 to 40 % had no effect on the production of secondary organic aerosol in the case of 2,5-dihydrofuran, while it reduced the particle number and particle mass concentrations from the 2,3-dihydrofuran ozonolysis. The waterto-SO 2 rate constant ratio for the 2,3-dihydrofuran Criegee intermediate was derived from the secondary organic aerosol (SOA) yields in experiments with different relative humidity values, k H 2 O /k SO 2 = (9.8 ± 3.7) × 10 −5 .The experimental results show that SO 3 may not be the only intermediate involved in the formation or growth of new particles in contrast to the data reported for other Criegee intermediate-SO 2 reactions. For the studied reactions, SO 2 concentrations remained constant during the experiments, behaving as a catalyst in the production of condensable products.Computational calculations also show that the stabilised Criegee intermediates from the ozonolysis reaction of both 2,5-dihydrofuran and 2,3-dihydrofuran may react with SO 2 , resulting in the regeneration of SO 2 and the formation of lowvolatility organic acids.

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“…Experimental results (Table 1) show that CH 2 OO and anti-CH 3 CHOO react with water vapor very quickly (3,(22)(23)(24). Thus, their steady-state concentrations would be too low to have a significant impact in SO 2 oxidation under typical atmospheric conditions, as shown in modeling results (15,16).…”

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confidence: 95%

Kinetics of a Criegee intermediate that would survive high humidity and may oxidize atmospheric SO ₂

Huang

Chao

Lin

2015

Proc. Natl. Acad. Sci. U.S.A.

228

276

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Criegee intermediates are thought to play a role in atmospheric chemistry, in particular, the oxidation of SO 2 , which produces SO 3 and subsequently H 2 SO 4 , an important constituent of aerosols and acid rain. However, the impact of such oxidation reactions is affected by the reactions of Criegee intermediates with water vapor, because of high water concentrations in the troposphere. In this work, the kinetics of the reactions of dimethyl substituted Criegee intermediate (CH 3 ) 2 COO with water vapor and with SO 2 were directly measured via UV absorption of (CH 3 ) 2 COO under near-atmospheric conditions. The results indicate that (i) the water reaction with (CH 3 ) 2 COO is not fast enough (k H2O < 1.5 × 10 −16 cm 3 s −1 ) to consume atmospheric (CH 3 ) 2 COO significantly and (ii) (CH 3 ) 2 COO reacts with SO 2 at a near-gas-kinetic-limit rate (k SO2 = 1.3 × 10 −10 cm 3 s −1 ). These observations imply a significant fraction of atmospheric (CH 3 ) 2 COO may survive under humid conditions and react with SO 2 , very different from the case of the simplest Criegee intermediate CH 2 OO, in which the reaction with water dimer predominates in the CH 2 OO decay under typical tropospheric conditions. In addition, a significant pressure dependence was observed for the reaction of (CH 3 ) 2 COO with SO 2 , suggesting the use of low pressure rate may underestimate the impact of this reaction. This work demonstrates that the reactivity of a Criegee intermediate toward water vapor strongly depends on its structure, which will influence the main decay pathways and steady-state concentrations for various Criegee intermediates in the atmosphere. Ozonolysis of unsaturated hydrocarbons produces highly reactive Criegee intermediates (CIs) (1), which may (i) decompose to radical species like OH radicals or (ii) react with a number of atmospheric species, for example, with SO 2 to form SO 3 and with NO 2 to form NO 3 (2, 3). The SO 2 oxidation by CIs has gained special attentions because the SO 3 product would be converted into H 2 SO 4 , an important constituent of aerosols and acid rain (4-8). For example, Mauldin et al. (4) (2) demonstrated an efficient method to prepare a CI in a laboratory by the reaction of iodoalkyl radical with O 2 (for example, CH 2 I + O 2 → CH 2 OO + I). This method can produce a CI of high enough concentration that allows direct detection. With photoionization mass spectrometry (PIMS) detection, Welz et al. (2) measured the rate coefficients of the simplest CI (CH 2 OO) reactions with SO 2 and NO 2 . Notably, these new rate coefficients, confirmed by a few later investigations (9-11), are orders of magnitude larger than those previously used (12, 13) in atmospheric models (e.g., MCM v3.3, available at mcm.leeds. ac.uk/MCM/browse.htt?species=CH2OO), suggesting a greater role of CIs in atmospheric chemistry. This result also indicates previous ozonolysis analyses may be affected by complicated and partly unknown side reactions and may contain errors in some of the reported rate coefficients.Typical...

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Competing atmospheric reactions of CH₂OO with SO₂and water vapour

Cited by 99 publications

References 39 publications

Reactivity of stabilized Criegee intermediates (sCIs) from isoprene and monoterpene ozonolysis toward SO<sub>2</sub> and organic acids

Reactivity of stabilized Criegee intermediates (sCIs) from isoprene and monoterpene ozonolysis toward SO<sub>2</sub> and organic acids

Formation of secondary organic aerosols from the ozonolysis of dihydrofurans

Kinetics of a Criegee intermediate that would survive high humidity and may oxidize atmospheric SO ₂

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Competing atmospheric reactions of CH2OO with SO2and water vapour

Cited by 99 publications

References 39 publications

Reactivity of stabilized Criegee intermediates (sCIs) from isoprene and monoterpene ozonolysis toward SO&lt;sub&gt;2&lt;/sub&gt; and organic acids

Reactivity of stabilized Criegee intermediates (sCIs) from isoprene and monoterpene ozonolysis toward SO&lt;sub&gt;2&lt;/sub&gt; and organic acids

Formation of secondary organic aerosols from the ozonolysis of dihydrofurans

Kinetics of a Criegee intermediate that would survive high humidity and may oxidize atmospheric SO 2

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Competing atmospheric reactions of CH₂OO with SO₂and water vapour

Reactivity of stabilized Criegee intermediates (sCIs) from isoprene and monoterpene ozonolysis toward SO<sub>2</sub> and organic acids

Reactivity of stabilized Criegee intermediates (sCIs) from isoprene and monoterpene ozonolysis toward SO<sub>2</sub> and organic acids

Kinetics of a Criegee intermediate that would survive high humidity and may oxidize atmospheric SO ₂