AlmractWe have performed magnetoresistance measurements up to 20 T on high-mobility two-dimensional electron gases in single AlAs quantum webs with well widths ranging from 40 to 80 A. We observe a sharp transition from a two-fold valley degenerate X~ occupied state in a 60 JL well to a non-degenerate X, occupied state in a 40 JL well These two states are distinguished by their diff~e~t effective masses, which have been determined using the temperature dependence of the Shubnikov--de I-ISL~ effect. Using self-consistent calculations, we can explain ~ Uanmtion in relative occupation assmning an X-splitting energy of 24 meV. Furthermore, for the X~ electrons, the effect of the ls.rge ratio of spin to Landau splitting is shown by the o~urrence of strong magnetoresistance minima at filling factors 2, 6 and 10 in the Hall effect.