In this study synchrotron X-ray absorption spectroscopy (XAS) has been applied, an element specific technique which allows Fe-containing phases to be identified in the complex mineral mixture of hydrated cements. Several Fe species contributed to the overall Fe K-edge spectra recorded on the cement samples. In the early stage of cement hydration ferrite was the dominant Fe-containing mineral. Ferrihydrite was detected during the first hours of the hydration process. After I day the formation of Al- and Fe-siliceous hydrogamet was observed, while the amount of ferrihydrite decreased. The latter finding agrees with thermodynamic modeling, which predicts the formation of Fe-siliceous hydrogarnet in Portland cement systems. The presence of Al- and Fe-containing siliceous hydrogarnet was further substantiated in the residue of hydrated cement by performing a selective dissolution procedure. (C) 2014 Elsevier Ltd. All rights reserved.