A method to be used in conjunction with a single-stage or multi-stage process for leaching ash originating from the recovery boiler of a pulp mill, particularly when the ash contains a significant amount of carbonate, wherein calcium compounds, such as calcium oxide (CaO) or calcium hydroxide (Ca(OH)2), are employed as additives in one or more leaching stages, a liquid fraction formed in the leaching process is utilized outside the main chemical recovery cycle, such as a substitute for purchased sodium hydroxide in the bleaching line of the pulp mill, and a solids fraction may be mixed with a black-liquor stream of the mill or subjected to further processing to separate calcium compounds for recycle.