The presence of sulfates in water or soils surrounding portland cement concrete structures leads to progressive degradation. Spatially resolved energy dispersive diffraction (EDXRD) in combination with computed microtomography (μCT) and mechanical measurements can provide the information needed to understand, in detail, the degradation mechanisms that are associated with sulfate attack and to validate accelerated test methods used to evaluate the sulfate resistance of cements. Highly penetrating, high-energy X-rays from synchrotron sources allow the use of EDXRD to nondestructively determine depth profiles for the crystalline phases in the cement paste specimens several millimeters below the sample surface. These depth profiles, and how they vary with sulfate exposure conditions and duration, can be correlated with mechanical changes and the crack patterns seen in the microtomographs. Spatially resolved EDXRD is in principle useful for phase composition mapping and depth profiling in a wide range of materials where the attenuation of high energy x-rays is not extreme. Suitable materials include many ceramic compositions.