Ken, there were the PFS (Planetary Fourier Spectrometer) observations around 2003 and ground-based spectral observations. Currently, the European Space Agency-Roscosmos ExoMars Trace Gas Orbiter is successfully orbiting Mars. One of the main goals of this space mission is more precise measurements of methane in the Martian atmosphere.
Ken, in connection with your question to me, you can read my article, which is here on Research Gate: N.S. Duxbury · S.S. Abyzov · V.E. Romanovsky · K Yoshikawa, A combination of radar and thermal approaches to search for methane clathrate in the Martian subsurface,
Hi Ken. Based on terrestrial analogs (we have nothing else to calibrate against) CH4 is plausibly of biological origin. 97% of methane on Earth is biogenic. Of course, we don't know now for sure the source for Martian methane.