The pulsed power operation mode of a radiofrequency (rf) glow discharge time-of-flight mass spectrometer was investigated, for several ions, in terms of intensity profiles along each pulse period. Particular attention was paid to the plateau and transient afterglow regions. An rf pulse period of 4 ms and a duty cycle of 50% was selected to evaluate the influence of discharge parameters in the afterglow delay and shape of Ar(+), Ar(2)(+) and several analytes (Br, Cl, Cu) contained in polymeric layers. Pulse shapes of Ar(+) and Ar(2)(+) ions vary with pressure and power. At low pressures the highest intensity is observed in the plateau while at higher pressures (>600 Pa) the afterpeak is the dominant region. Although the influence of the applied power is less noticeable, a widening of the afterglow time regime occurs for Ar(+) when increasing the power. Maximum intensity of the argon signal is measured in the afterglow at 30 W, while the area of such afterpeak increases with power. The maximum intensity of Ar(2)(+) is obtained at the highest power employed (60 W) and the ratio maximum intensity/afterglow area remains approximately constant with power. Analytes with ionization potentials below (Cu) or just above (Br) the argon metastable energy show maxima intensities after argon ions decay, indicating they could be ionized by collisions with metastable Ar atoms. Chlorine signals are observed in the afterglow despite their ionization potential is well above the energy of argon metastable levels. Moreover, they follow a similar pattern to that observed for Ar(2)(+) , indicating that charge-transfer process with Ar(2)(+) could play a significant role.

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