This study looks at the interactions between simulated calcined high level waste from fuel reprocessing and mixed alkali borosilicate glass frit in the early stages of melting, and the possibility of the formation of yellow phase during these stages. Simulant “calcine” from a full scale inactive trial (Magnox: oxide “blend” 25:75) was pre-mixed with alkali borosilicate glass, to achieve a 25wt% waste loading, and melted at 1050°C at various times. It is shown that dissolution occurs in two separate stages; the first involves formation of a low density CsLiMoO4 fluid, which separates and forms a yellow/green layer on the surface of the melt, accompanied by some dissolution of rare- earth elements (Nd, Ce, Gd) and Zr from the waste into the glass matrix. The second stage entails more extensive migration of these rare-earth elements into the glass, and the disappearance of the surface layer on the melt. The glass appears more homogenized at the later stages of melting, but still contains undissolved particles of calcine after 16 minutes.