Raman diagnostic of the reactivity between ZnSO4 and CaCO3 particles in humid air relevant to heterogeneous zinc chemistry in atmosphere
Résumé
Laboratory experiments using Raman imaging demonstrated the behaviour of ZnSO4⋅7H2O (goslarite) microparticles in contact with a 1014 CaCO3 (calcite) surface under three different experimental conditions representative of remote atmosphere. Contact between the ZnSO4⋅7H2O particles and the CaCO3 surface in humid air (RH ~40-80%) did not induce any deliquescence and chemical phenomena. In contrast, condensation of a water drop at the ZnSO4⋅7H2O-CaCO3 interface caused free dissolution of the ZnSO4⋅7H2O particle and rapid precipitation of Zn4SO4(OH)6 onto the CaCO3 surface. This coating inhibited the surface reaction and subsequent drying resulted in the deposition of residual ZnSO4⋅7H2O, then ZnSO4⋅H2O (gunningite) and CaSO4⋅2H2O (gypsum) superimposed onto the Zn4SO4(OH)6 layer. The deposition of ZnSO4⋅7H2O particles in a water drop, previously in contact with a CaCO3 particle for a long time, resulted in the coprecipitation of Zn4SO4(OH)6 and Zn5(CO3)2(OH)6 (hydrozincite). Subsequent drying caused the deposition of residual ZnSO4⋅7H2O, ZnSO4⋅H2O and CaSO4⋅2H2O as small particles. These results indicated the possible fates of ZnSO4 particles in a humid atmosphere, when externally mixed with CaCO3 mineral dust after atmospheric events such as aggregation, water condensation and evaporation. This study indicated the fundamental role of water that typically existed on the surface of aerosol particles in the troposphere. These heterogeneous chemical processes have substantial consequences on particle size and solubility, and thus on bioavailability and toxicity of metal-rich particles.