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The Cl-initiated oxidation of CH3C(O)OCH=CH2, CH3C(O)OCH2CH=CH2, and CH2=CHC(O)O(CH2)3CH3 in the troposphere

  • AREA 3 • ATMOSPHERIC CHEMISTRY AND PHYSICS • RESEARCH ARTICLE
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Abstract

Background, aim, and scope

Unsaturated esters are emitted to the atmosphere from biogenic and anthropogenic sources, including those from the polymer industry. Little information exists concerning the atmospheric degradation of unsaturated esters, which are mainly initiated by OH radicals. Limited information is available on the degradation of alkenes by Cl atoms and almost no data exists for the reactions of unsaturated esters with Cl atoms. This data is necessary to assess the impact of such reactions in maritime environments where, under circumstances, OH radical- and Cl atom-initiated oxidation of the compounds can be important. Rate coefficients for the reactions of chlorine atoms with vinyl acetate, allyl acetate, and n-butyl acrylate have been determined at 298 ± 3 K and atmospheric pressure. The kinetic data have been used in combination with that for structurally similar compounds to infer the kinetic contributions from the possible reaction channels to the overall reaction rate.

Materials and methods

The decay of the organics was followed using in situ Fourier transform infrared spectroscopy and the rate coefficients were determined using a relative kinetic method and different hydrocarbon reference compounds.

Results

The following room temperature rate coefficients (in cm3 molecule−1 s−1) were obtained: k 1 (Cl + CH3C(O)OCH=CH2) = (2.68 ± 0.91) × 10−10, k 2 (Cl + CH3C(O)OCH2CH=CH2) = (1.30 ± 0.45) × 10−10, and k 3 (Cl + CH2=CHC(O)O(CH2)3CH3) = (2.50 ± 0.78) × 10−10, where the uncertainties are a combination of the 2σ statistical errors from linear regression analyses and a contribution to cover uncertainties in the rate coefficients of the reference hydrocarbons.

Discussion

This is the first kinetic study of the title reactions under atmospheric conditions. The kinetic data were analyzed in terms of reactivity trends and used to estimate the atmospheric lifetimes of the esters and assess their potential importance in the marine atmosphere.

Conclusions

Although reaction with OH radicals is the major atmospheric sink for the unsaturated esters studied, reaction with Cl atoms can compete in the early morning hours in coastal areas where the Cl concentration can reach peak values as high as 1 × 105 atoms cm−3. The calculated residence times show that the chemistry of unsaturated esters will impact air quality locally near their emission sources.

Recommendations and perspectives

The reactions need to be studied over the range of temperatures and pressures generally encountered in the marine atmosphere. In addition, product studies should also be performed as a function of temperature since this will allow degradation mechanisms to be derived, which are representative for the wide range of conditions occurring in marine environments. Inclusion of the kinetic and product data in tropospheric numerical models will allow an assessment of potential environmental impacts of the esters for different marine pollution scenarios.

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Acknowledgements

The authors wish to acknowledge DAAD–PROALAR (Germany), the Deutsche Forschungsgemeinschaft (DFG), the EU project EUROCHAMP, SECYT (Argentina), CONICET (Argentina), ANPCyT–FONCYT (Argentina), SECyT–UNC (Córdoba, Argentina), Fundación Antorchas (Argentina), TWAS (Italy), and RSC (UK) for financial support of this research.

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Authors and Affiliations

  1. Instituto de Investigaciones en Fisicoquímica de Córdoba (I.N.F.I.Q.C.), Dpto. de Fisicoquímica, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Ciudad Universitaria, 5000, Córdoba, Argentina

    María B. Blanco & Mariano A. Teruel

  2. FB C—Physikalische Chemie, Bergische Universität Wuppertal, 42097, Wuppertal, Germany

    Iustinian Bejan, Ian Barnes & Peter Wiesen

  3. Faculty of Inorganic and Analytical Chemistry, ‘Al. I. Cuza’ University of Iasi, Iasi, Romania

    Iustinian Bejan

Authors
  1. María B. Blanco
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  2. Iustinian Bejan
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  3. Ian Barnes
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  4. Peter Wiesen
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  5. Mariano A. Teruel
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Corresponding author

Correspondence to Mariano A. Teruel.

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Responsible editor: Gerhard Lammel

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Blanco, M.B., Bejan, I., Barnes, I. et al. The Cl-initiated oxidation of CH3C(O)OCH=CH2, CH3C(O)OCH2CH=CH2, and CH2=CHC(O)O(CH2)3CH3 in the troposphere. Environ Sci Pollut Res 16, 641–648 (2009). https://doi.org/10.1007/s11356-008-0096-y

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  • DOI: https://doi.org/10.1007/s11356-008-0096-y

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