H-2 MAS NMR spectroscopy was applied to study the deuterated form of iron oxyhydroxide goethite (alpha-FeOOD), typically one of the major inorganic components of soil. High-resolution spectra can be obtained above the Neel temperature, either by raising the temperature or by cation doping. The results indicate that NMR spectroscopy is a feasible method for characterizing the local internal and surface structures of these classes of materials and challenge the often-held assumption that iron-containing materials are impossible to investigate by using high-resolution MAS NMR methods.