In this work we present the investigations on the blackening of the outer jacket of the High Pressure Sodium (HPS) lamps. For this purpose ceramic arc tubes and their glass outer jackets taken from lamps burned for different times (0h-10000h) were examined by X-ray Photoelectron Spectroscopy (XPS) and Secondary Ion Mass Spectroscopy (SIMS) in order to determine the composition of the deposit on the internal wall of glass outer jacket. In the case of the several thousand hours burned lamps the outer bulb was found to be covered by aluminium, which comes to a black deposit on the glass surface. XPS identified Al on the glass surface can be found in two different chemical state (elemental Al, Al(2)O(3)). The assumed evaporation of aluminium-oxide ceramic tube might be described by a dissociative mechanism of the alumina evaporation. This papers described the possible mechanism of the alumina evaporation. Na was also found in the black deposit, whose cause of this in the case of the several thousand hours burned lamps is probably related to the sodium transport through the walls of the arc tube.