A new generation of electronic cigarettes is exacerbating the youth vaping epidemic by incorporating additives that increase the acidity of generated aerosols, which facilitate uptake of high nicotine levels. We need to better understand the chemical speciation of vaping aerosols to assess the impact of acidification. Here we used X-ray photoelectron spectroscopy (XPS) and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy to probe the acid-base equilibria of nicotine in hydrated vaping aerosols. We show that, unlike the behavior observed in bulk water, nicotine in the core of aqueous particles was partially protonated when the pH of the nebulized solution was 10.4, with a fraction of free-base nicotine (α_FB) of 0.34. Nicotine was further protonated by acidification with equimolar addition of benzoic acid (α_FB = 0.17 at pH 6.2). By contrast, the degree of nicotine protonation at the particle surface was significantly lower, with 0.72 < α_FB < 0.80 in the same pH range. The presence of propylene glycol and glycerol completely eliminated protonation of nicotine at the surface (α_FB = 1) while not affecting significantly its acid-base equilibrium in the particle core. These results provide a better understanding of the role of acidifying additives in vaping aerosols, supporting public health policy interventions.