Night-time oxidation at the air–water interface: co-surfactant effects in binary mixtures

Abstract

The ageing of organic-coated aqueous aerosols at night is investigated by reacting NO₃ with binary surfactant mixtures floating on water. The surfactants are oleic acid (OA), methyl oleate (MO) and stearic acid (SA). Deuterated surfactants mixed with hydrogenous surfactants were studied using neutron reflectometry to determine the reaction kinetics of organic two-component monolayers with NO₃ at the air–water interface for the first time. We measured the rate coefficients for OA monolayers, mixed with hydrogenous co-surfactant MO or SA to be (3 ± 1) × 10⁻⁸ cm² per molecule per s or (3.6 ± 0.9) × 10⁻⁸ cm² per molecule per s and MO monolayers mixed with hydrogenous co-surfactant OA or SA to be (0.7 ± 0.4) × 10⁻⁸ cm² per molecule per s or (3 ± 1) × 10⁻⁸ cm² per molecule per s. The initial desorption lifetimes of NO₃, τ_d,NO3,1, were 8 ± 3 ns, 14 ± 4 ns, 12 ± 3 ns and 21 ± 10 ns. The approximately doubled desorption lifetime for MO–SA compared to the other mixtures is consistent with a more accessible double bond associated with the larger area per molecule of MO in the presence of SA facilitating NO₃ attack. The significantly slower reactive loss of MO–OA compared to a MO monolayer demonstrates that multi-component surfactant mixtures need to be studied in addition to single-component monolayers. Such a retarded decay would cause the residence time to change from ca. 4 to 22 minutes associated with increased transport distances of surfactant species together with any other pollutants that may be protected underneath the surfactant film.