This work evaluated the combination of ozone and activated sludge for treatment of bleached kraft pulp effluents. Ozonation was done before and after biological treatment. First the influence of pH, temperature and hydrogen peroxide dose on ozonation was assessed in order to optimize treatment efficiency, which was evaluated in terms of COD, BOD5, lignin, biodegradability and toxicity. After the preliminary assessments and definition of conditions, ozonation was run as pre-treatment and as intermediate treatment between biological treatments. Results showed that neither pH nor temperature played an important role in COD removal and increasing BOD5 and biodegradability, suggesting that is not necessary to adjust temperature and pH before ozone application. Although addition of hydrogen peroxide improved biodegradability, it left a residual that is toxic to biological treatment and would have to be eliminated. The effluent contained a hydrogen peroxide residual of 0.7 mmol L-1 due the use of this reagent as a bleaching agent at the mill. Given that ozonation (2; 5 and 10 mmol L-1) without addition of hydrogen peroxide led to a 50% increase in biodegradability it was decided not to add hydrogen peroxide to the effluents in further experiments. Pre- treatment with ozone followed by biological treatment improved COD, TOC, AOX and lignin removals. The effects of ozonation and biological treatment on low and high molecular weight compounds were also assessed, by filtration at a membrane of 500 g mol-1 cut off. It was observed that organic matter removal was much more efficient in the low molecular weight fraction (< 500 g mol-1) and that the majority of recalcitrant organic matter is in the high molecular weight fraction (> 500 g mol-1). The last part of the work assessed the use of ozone as intermediate treatment, between aerobic biological treatments and the influence of the hydraulic retention time (HRT) on removal of the analyzed parameters. Samples were collected in the mill biological reactor at different theoretical HRT (1.2; 2.3; 3.5; 7 and 14 hours) and in the bench-scale laboratory reactor operated at different HRT (2; 4; 8 and 12 hours). In both the industrial and laboratory systems the majority of organic matter was removed within the first two hours of treatment, although higher removals were achieved at HRT greater than seven hours. Effluent treated in the laboratory two and four hours were treated with ozone doses of 2; 5 and 10 mmol L-1. Post-ozonation was efficient in removal of color and lignin, but had limited potential for the removal of COD and TOC. BOD5 increased, suggesting that a subsequent biological treatment would improve overall organic matter removal, but BOD5 after ozonation was at most 30 mg L-1, only half the legal limit for discharge, and further biological treatment was not attempted. Use of ozone as an intermediate after aerobic biological treatment was not a viable alternative for COD reduction, but would be very efficient if the aim was to remove color and lignin.
