Ionic strength effect on the formation of organonitrate compounds through photochemical degradation of vanillin in liquid water of aerosols

Abstract

The ionic strength can affect the photochemical reactions occurring in the liquid core of the aerosol deliquescent particles. Yet, the investigations related to ionic strength effect on aqueous-phase reactions are limited. Here we assess the photochemical degradation of a typical lignin-derived compound, vanillin (VL), upon addition of either sodium nitrate (NaNO3) or sodium sulfate (Na2SO4). The UV-VIS absorption spectra of VL exhibits a hyperchromic effect and a bathochromic shift of the n→π* absorption band, in going from λmax = 310 nm in the dilute aqueous phase to λmax = 346 nm at I = 0.3 M adjusted by Na2SO4. A hypsochromic shift of the n→π* absorption band of VL, in going from λmax = 310 nm in the dilute liquid water to λmax = 303 nm at Ieff = 0.124 M is observed when the ionic strength was adjusted with NaNO3.At fixed pH ≈ 4, representing both the cloud droplets and the liquid core of the aerosol particles, the pseudo-first-order rate constant, k1st (Ieff.→0) = (1.5 ± 0.2) x 10−5 s−1, in dilute aqueous solution (Ieff = 0 M, NaNO3), linearly decreases to (k1st = (3.7 ± 0.2) x 10−6 s−1), at Ieff = 0.124 M (NaNO3) with kinetic salting coefficient b = -(4.8 ± 0.2) L mol−1. The very subtle pH change of the absorption spectra of irradiated VL is observed due to the formation of carboxylic acids, hydroxylated compounds and oligomers which presence was confirmed by FT-ICR MS analysis. Most likely aliphatic like CHO compounds are formed upon photodegradation of VL in dilute aqueous phase while the condensed aromatic CHO and CHON compounds are produced in presence of nitrate ions (Ieff = 0.124 M). These results suggest that inorganic ions present in the liquid water of aerosols alters the kinetics and the product formation of photochemical degradation of organic compounds which in turn can affect the light absorption properties of aerosols.