Experimental and Computational Investigations of the Tropospheric Photooxidation Reactions of 1,1,1,3,3,3-Hexafluoro-2-Methyl-2-Propanol Initiated by OH Radicals and Cl Atoms.

The gas-phase kinetics for the reactions of OH radicals and Cl atoms with 1,1,1,3,3,3-hexafluoro-2-methyl-2-propanol (HF2M2P) were measured at temperatures between 268 and 363 K using the relative rate experimental technique. Methane and acetonitrile were used as reference compounds to measure the rate coefficients of the title reactions. For the reactions of HF2M2P with OH radicals and Cl atoms, the rate coefficients were measured to be (7.07 ± 1.21) × 10-15 and (2.85 ± 0.54) × 10-14 cm3 molecule-1 s-1, respectively, at 298 K. The obtained Arrhenius expressions for the reactions of HF2M2P with OH radicals and Cl atoms are kHF2M2P + OHExp - (268 - 363 K) = (7.84 ± 0.75) × 10-14 exp [-(717 ± 59)/T] and kHF2M2P + ClExp - (268 - 363 K) = (3.21 ± 0.45) × 10-12 exp [-(1395 ± 83)/T] cm3 molecule-1 s-1. In addition to the experimental measurements, computational kinetic calculations were also performed for the title reactions at the M06-2X/MG3S//M06-2X/6-31 + G(d,p) level of theory using advanced methods such as the canonical variational transition-state theory coupled with small curvature tunneling corrections at temperatures between 200 and 400 K. Theoretical calculations reveal that the H-abstraction from the CH3 group is a more favorable reaction channel than that from the OH group. Thermochemistry, branching ratios, cumulative atmospheric lifetime, global warming potential, acidification potential, and photochemical ozone creation potential of HF2M2P were calculated in the present investigation.

Water-soluble organic aerosols over South Asia - Seasonal changes and source characteristics.

Water-soluble organic carbon (WSOC) has been identified as a key component in atmospheric aerosols due to its ability to act as cloud condensation nuclei (CCN) owing to their highly hygroscopic nature. This paper discusses about the spatio-temporal variability in WSOC mass concentration, sources (primary and secondary contributions), the role of long-range air-mass transport in modulating their abundance, at distinct sectors over South Asia. We found from our observations that, photochemical ageing of primary organic aerosols that are derived from biomass emissions, significantly contribute to the total WSOC budget over South Asia. The wide range of water-soluble compounds released by biomass burning can contribute directly to the WSOC fraction or undergo further atmospheric processing, such as oxidation or ageing, leading to the formation of additional WSOC. WSOC/OC (organic carbon) ratio and the correlation between the WSOC and secondary organic carbon (SOC) are used for assessing the contribution from secondary sources. The three different ratios are used to delineate different source processes; OC/EC (elemental carbon) for source identification, WSOC/OC for long-range atmospheric transport (ageing) and WSOC/SOC to understand the primary and secondary contribution of WSOC. The present investigation revealed that, the primary OC that have undergone significant chemical processing as a result of long-range transport have a substantial influence on WSOC formation over South Asia, especially in Indo Gangetic Plain outflow regions such as southern peninsular and adjacent marine regions. Overall, oxidation and ageing of primary organic aerosols emitted from biomass burning was found to serve as an important source of WSOC over South Asia.