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Abstract: The role of transition metals in oxidative degradation of cellulose has been studied. Degradation experiments with model papers and studies of hydroxyl radical production in solution have been performed with Fe, Cu, Mn, Co, Cr, Ni, and Zn. Rates of production of hydroxyl radicals in solution have been estimated using the radical scavenger N,N′-(5-nitro-1,3-phenylene)bisglutaramide in the pH interval 7–9. Hydroxyl radical production during degradation of Cu-containing cellulose has been studied. To gain a better insight into chemistry behind degradation processes, chemiluminometric experiments were also performed. The experiments provide strong evidence that the role of transition metals during the oxidative degradation of cellulose is catalytic. A correlation between the behaviour of transition metals in solution and in paper was established at low contents of transition metal in paper. [Copyright &y& Elsevier]