Chemo and fire assay with certified result is the only way, and even then...there can be uncertainty. The richest Rh bearing ore I ever found myself was Au-Rh from a mother lode vein, and the Rh was 8%, other PGMs, Ag, O2, Cu, Ar, Sn, Su, Te were present. The Au-Rh alloys were in a complex stone matrix that included Kimberlite. PGM/Ag and Au rich nuggets were strewn about on the surface, very metallic. The immediate tests were malleability and ductility, acids. They showed a back pack full of samples were justified for me to hike back a day to my base camp and get to work. I still hold the claim and work it. I invested in valid assays, XRF for ores seldom cuts it.