Using high-resolution and spin-lattice relaxation MAS Al-27 NMR methods, we obtained structural information about Al species in steamed Y zeolites that are intermediate between NMR-detectable tetrahedral and octahedral Al species. The Al species, NMR shifted from aluminum nitrate aqueous solution at about 30 ppm, responded to various chemical and physical sample treatments dramatically differently than the tetrahedral framework and octahedral extraframework Al sites. Spin-lattice relaxation resolves at least two new peaks, previously unreported, near the 30 ppm peak. The T-1 relaxation times of the 30 ppm Al sites are also different from the tetrahedral and octahedral Al sites. These experimental results lead to a conclusion that the 30 ppm peak reported previously is actually a mixture of extraframework Al species. The results are of fundamental importance in understanding steamed zeolite structures and in quantifying catalytically active sites. This work illustrates how sample treatment and spin relaxation can provide additional "resolution" to NMR spectroscopy of a complex solid material. It also serves as a reminder that the structure of steamed zeolites is more diverse than previously thought.