Volcanic gases contain ultrafine aerosol particles in the nanometer size range; typical concentrations are 105 to 106 cm-3. Photoelectric charging of particles (PCP) as an in situ method for the material specific detection of very small particles in a gas. Field studies at degassing lava flows of Mount Etna, Sicily, and Kilauea, Hawaii, show that the chemistry of the ultrafine aerosols depends strongly on the degassing state of the lava. Heating of a relatively undegassed lava sample in the laboratory reveals the chemical nature of the particles that form by nucleation and condensation in the cooling gas. In the initial stages of degassing, the particles are mainly NaCl and KCl nanocrystals that contain iron oxide and copper chloride. Cu is in the monovalent state, which is stable even in an oxidizing environment due to a redox mechanism with the Fe ions. The fraction of Cu(I) in the aerosols is determined by PCP. The evolution of the Cu(I) fraction is considered an effective tracer of chlorides in the magmatic gases and thereby of magma degassing. The PCP technique allows a fingerprint to be obtained of the magmatic gas by an aerosol measurement in the diluted plume. ¿ American Geophysical Union 1993