Laboratory experiments using in situ Raman imaging combined with ex situ TOF-S-SIMS demonstrate the behavior of CdSO₄*8/3H₂O microparticles in contact with { 1014 } CaCO₃ (calcite) surface under three different experimental conditions representative of unpolluted atmosphere. The contact of CdSO₄*8/3H₂O particles with CaCO₃ surface in humid air (RH ∼ 40-80%) does not induce any chemical reaction. In contrast, the condensation of a water drop on CdSO₄*8/3H₂O/CaCO₃ interface causes the free dissolution of CdSO₄*8/3H₂O particle in the drop. A CdSO₄*8/3H₂O microcrystal is reformed after gentle drying with a CdSO₄*H₂O coating of the CaCO₃ surface. The TOF-S-SIMS image of the CaCO₃ surface provides evidence of a thin layer corresponding probably to insoluble coating of CdCO₃ (otavite) or Cd_xCa₁−_xCO₃ solid solution at the liquid-solid interface. This layer armours the CaCO₃ from further dissolution and stops the reaction. The deposition of CdSO₄*8/3H₂O particle in water drop previously in contact with CaCO₃ for a long time generates CdCO₃ small rhombohedral crystals while gentle drying provokes the crystallization of bar shape crystals of CaSO₄*2H₂O (gypsum). These laboratory results provide valuable chemical prediction for a possible fate of cadmium rich particles emitted in the atmosphere and thus, can contribute to realistic assessment of human exposure to Cd hazard.