The solid solution between Al- and Fe-ettringite Ca-6[Al1-xFex(OH)(6)](2)(SO4)(3)center dot 26H(2)O was investigated. Ettringite phases were synthesized at different Al/(Al + Fe)-ratios (=X-Al,X-total), so that X-Al increased from 0.0 to 1.0 in 0.1 unit steps. After 8 months of equilibration, the solid phases were analyzed by X-ray diffraction (XRD) and thermogravimetric analysis (TGA), while the aqueous solutions were analyzed by inductively coupled plasma optical emission spectroscopy (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-MS). XRD analyses of the solid phases indicated the existence of a miscibility gap between X-Al,X-total =0.30-0.6. Some of the XRD reflections showed two overlapping peaks at these molar ratios. The composition of the aqueous solutions, however, would have been in agreement with both, the existence of a miscibility gap or a continuous solid solution between Al- and Fe-ettringite, based on thermodynamic modeling, simulating the experimental conditions. (c) 2009 Elsevier Ltd. All rights reserved.