We probe, at high energy resolution, the double electron excitation (KLII&II) X-ray absorption region that lies approximately 115 eV above the main Al K-edge (1566 eV) of alpha-alumina and sodium aluminate. The two solid standards, alpha-alumina (octahedral) and sodium aluminate (tetrahedral), are compared to aqueous species that have the same Al coordination symmetries, Al3+center dot 6H(2)O (octahedral) and Al(OH)(4)(-) (tetrahedral). For the octahedral species, the edge height of the KLII&III-edge is approximately 10% of the main K-edge; however, the edge height is much weaker (3% of K-edge height) for Al species with tetrahedral symmetry. For the a-alumina and aqueous Al3+center dot 6H(2)O the KLII&III spectra contain white line features and extended absorption fine structure (EXAFS) that mimics the K-edge spectra. The KLII&III-edge feature interferes with an important region in the EXAFS spectra of the crystalline and aqueous standards. The K-edge spectra and K-edge energy positions are predicted using time-dependent density functional theory (TDDFT). The TDDFT calculations for the K-edge X-ray absorption near-edge spectra (XANES) reproduce the observed transitions in the experimental spectra of the four Al species. The KLII&II and KLI onsets and their corresponding chemical shifts for the four standards are estimated using the delta self-consistent field (Delta SCF) method.