Kinetic and Products Study of the Atmospheric Degradation of trans-2-Hexenal with Cl Atoms.

The gas-phase reaction between trans-2-hexenal (T2H) and chlorine atoms (Cl) was studied using three complementary experimental setups at atmospheric pressure and room temperature. In this work, we studied the rate constant for the titled oxidation reaction as well as the formation of the gas-phase products and secondary organic aerosols (SOAs). The rate constant of the T2H + Cl reaction was determined using the relative method in a simulation chamber using proton-transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS) to monitor the loss of T2H and the reference compound. An average reaction rate constant of (3.17 ± 0.72) × 10-10 cm3 molecule-1 s-1 was obtained. From this, the atmospheric lifetime of T2H due to Cl reaction was estimated to be 9 h for coastal regions. HCl, CO, and butanal were identified as primary products using Fourier transform infrared spectroscopy (FTIR). The molar yield of butanal was (6.4 ± 0.3)%. Formic acid was identified as a secondary product by FTIR. In addition, butanal, 2-chlorohexenal, and 2-hexenoic acid were identified as products by gas chromatography coupled to mass spectrometry but not quantified. A reaction mechanism is proposed based on the observed products. SOA formation was observed by using a fast mobility particle sizer spectrometer. The measured SOA yields reached maximum values of about 38% at high particle mass concentrations. This work exhibits for the first time that T2H can be a source of SOA in coastal atmospheres, where Cl concentrations can be high at dawn, or in industrial areas, such as ceramic industries, where Cl precursors may be present.

Gas-Phase Ozone Reaction Kinetics of C5-C8 Unsaturated Alcohols of Biogenic Interest.

Unsaturated alcohols are volatile organic compounds (VOCs) that characterize the emissions of plants. Changes in climate together with related increases of biotic and abiotic stresses are expected to increase these emissions in the future. Ozonolysis is one of the oxidation pathways that control the fate of unsaturated alcohols in the atmosphere. The rate coefficients of the gas-phase O3 reaction with seven C5-C8 unsaturated alcohols were determined at 296 K using both absolute and relative kinetic methods. The following rate coefficients (cm3 molecule-1 s-1) were obtained using the absolute method: (1.1 ± 0.2) × 10-16 for cis-2-penten-1-ol, (1.2 ± 0.2) × 10-16 for trans-2-hexen-1-ol, (6.4 ± 1.0) × 10-17 for trans-3-hexen-1-ol, (5.8 ± 0.9) × 10-17 for cis-3-hexen-1-ol, (2.0 ± 0.3) × 10-17 for 1-octen-3-ol, and (8.4 ± 1.3) × 10-17 for trans-2-octen-1-ol. The following rate coefficients (cm3 molecule-1 s-1) were obtained using the relative method: (1.27 ± 0.11) × 10-16 for trans-2-hexen-1-ol, (5.01 ± 0.30) × 10-17 for trans-3-hexen-1-ol, (4.13 ± 0.34) × 10-17 for cis-3-hexen-1-ol, and (1.40 ± 0.12) × 10-16 for trans-4-hexen-1-ol. Alkenols display high reactivities with ozone with lifetimes in the hour range. Rate coefficients show a strong and complex dependence on the structure of the alkenol, particularly the relative position of the OH group toward the C═C double bond. The results are discussed and compared to both the available literature data and four structure-activity relationship (SAR) methods.

An experimental study of the gas-phase reaction between Cl atoms and trans-2-pentenal: Kinetics, products and SOA formation.

The gas-phase reaction of trans-2-pentenal (T2P) with Cl atoms was studied at atmospheric pressure and room temperature. A rate coefficient of (2.56 ± 0.83) × 10-10 cm3 molecule-1 s-1 was obtained using the relative rate method and isoprene, cyclohexane and ethanol as reference compounds. The kinetic study was carried out using a 300-L Teflon bag simulation chamber (IMT Lille Douai-France) and a 16-L Pyrex cell (UCLM-Ciudad Real-Spain), both coupled to the Fourier transform infrared (FTIR) technique. Gas-phase products and secondary organic aerosol (SOA) formation were studied at UCLM using a 16-L Pyrex cell and a 264-L quartz simulation chamber coupled to the FTIR and gas-chromatography-mass spectrometry (GC-MS) techniques. HCl, CO, and propanal were identified as products formed from the studied reaction and quantified by FTIR, the molar yield of the latter being (5.2 ± 0.2)%. Formic acid was identified as a secondary product and was quantified by FTIR with a yield of (6.2 ± 0.4)%. In addition, 2-chlorobutanal and 2-pentenoic acid were identified, but not quantified, by GC-MS as products. The SOA formation was investigated using a fast mobility particle sizer spectrometer. The observed SOA yields reached maximum values of around 7% at high particle mass concentrations. This work provides the first study of the formation of gaseous and particulate products for the reaction of Cl with T2P. A reaction mechanism is suggested to explain the formation of the observed gaseous products. The results are discussed in terms of structure-reactivity relationship, and the atmospheric implications derived from this study are commented as well.

The reaction of hydroxyl and methylperoxy radicals is not a major source of atmospheric methanol.

Methanol is a benchmark for understanding tropospheric oxidation, but is underpredicted by up to 100% in atmospheric models. Recent work has suggested this discrepancy can be reconciled by the rapid reaction of hydroxyl and methylperoxy radicals with a methanol branching fraction of 30%. However, for fractions below 15%, methanol underprediction is exacerbated. Theoretical investigations of this reaction are challenging because of intersystem crossing between singlet and triplet surfaces - ∼45% of reaction products are obtained via intersystem crossing of a pre-product complex - which demands experimental determinations of product branching. Here we report direct measurements of methanol from this reaction. A branching fraction below 15% is established, consequently highlighting a large gap in the understanding of global methanol sources. These results support the recent high-level theoretical work and substantially reduce its uncertainties.