I would recommend PyMCA (http://pymca.sourceforge.net/index.html), it allows fitting of XRF data, and provided that your source characteristics are properly calibrated, quantitative analysis is also feasible. I cannot say it is the best freeware for XRF, however it is well suited to do all what one expects. Best regards, Dirk
In addition to my previous answer, fityk (fityk.nieto.pl) May also be of use. It is a standard fitting software not dedicated for a specific purpose, but for all kinds of fits…