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The speciation of U, Np, and Pu in Na-Al-(Fe)-phosphate glasses was studied by XAFS, XPS, and FTIR spectroscopy. At low UO2 content (5 wt.%) U(V) dominates over U(IV). At 5 to 10 wt.% UO3 U(V) and U(VI) contents are comparable. At higher UO3 content major U is present as U(VI) and minor as U(V) in the form of UO22+ and UO2+, respectively. Np was found to be predominantly tetravalent – Np(IV) while Pu(III) dominates over Pu(IV) in Fe free glass and on the contrary in the Fe bearing glass.