Recent Al-27 MAS NMR studies of hydrated Portland cements and calcium-silicate-hydrate (C-S-H) phases have shown a resonance from Al in octahedral coordination, which cannot be assigned to the well-known aluminate species in hydrated Portland cements. This resonance, which exhibits the isotropic chemical shift delta(iso) =5.0 ppm and the quadrupole product parameter P-Q = 1.2 MHz, has been characterized in detail by Al-27 MAS and Al-27{H-1} CP/MAS NMR for different hydrated white Portland cements and C-S-H phases. These experiments demonstrate that the resonance originates from an amorphous or disordered aluminate hydrate which contains Al(OH)(6)(3-) or OxAl(OH)(6-x)((3+x)-) units. The formation of the new aluminate hydrate is related to the formation of C-S-H at ambient temperatures, however, it decomposes by thermal treatment at temperatures of 70-90 degrees C. From the experiments in this work it is proposed that the new aluminate hydrate is either an amorphous/disordered aluminate hydroxide or a calcium aluminate hydrate, produced as a separate phase or as a nanostructured surface precipitate on the C-S-H phase. Finally, the possibilities of Al3+ for Ca2+ substitution in the principal layers and interlayers of the C-S-H structure are discussed. (c) 2005 Elsevier Ltd. All rights reserved.