The effect of introducing molecular compounds into argon plasmas has been studied using an expanding microwave induced plasma at atmospheric pressure. Besides the use of optical emission spectroscopy (OES), also the time dependent behavior of line intensities during power interruptions has been studied. From the measurements it is found that even an injection of small amounts of molecular compounds (> 0.5%) leads to important changes in excitation mechanisms in the plasma. It is also found that in the recombination zone downstream in the plasma an excitation mechanism which is independent of the electron density, e.g. excitation transfer from metastables or Penning ionization, must be responsible for the excitation of analytes.