The 'singularity' error is similar to what is discussed in this tech tip because the separability measurement also performs a matrix inversion:
http://www.exelisvis.com/...echtip.asp?ttid=3343
You might check the statistics of your input bands to be sure that there are no empty or duplicate bands, that your ROIs have variance, and that your ROIs have more points than the number of bands in the file.