Heterogeneous microchemistry between CdSO4 and CaCO3 particles under humidity and liquid water

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 101¯4 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 CdxCa1-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.