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Acid hydrogen peroxide catalyzed with molybdenum (PMo stage) is effective to decrease pulp kappa number and potentially minimize chlorine dioxide demand in subsequent ECF bleaching. This study aimed at developing cost-effective methods for applying PMo as the first stage bleaching for eucalyptus kraft pulp and evaluating their impact on pulp properties and effluent quality in relation to current ECF bleaching techniques. The PMo(EP)DP and A/PMo(EP)DP sequences proved to be most cost-effective for PMo stage application. The pulp properties and effluent quality derived from bleaching with these two sequences were compared with those of the conventional bleaching with the DHT(EP)DP sequence. The PMo(EP)DP sequence produced pulp of refinability and physical properties similar to that of the reference but the A/PMo(EP)DP one resulted in pulp of 20% lower refinability and 10% lower tearing strength. Untreated effluents of the PMo(EP)DP and A/PMo(EP)DP sequences presented similar COD, but lower AOX and color than the DHT(EP)DP effluents. None of the effluents exhibited acute toxicity. The effluents from the PMo(EP)DP sequence showed much lower BOD and BOD/COD ratio than that of the A/PMo(EP)DP one. All effluents were readily treated in bench-scale reactors, and achieved COD removal efficiencies of greater than 70%