The accumulation of calcium on biological activated carbon (BAC) and their effects on adsorption of synthetic organic chemicals (SOCs) were studied using BAC, which have been operated for 5 (BAC5.0) and 3.5 (BAC3.5) years in a pilot-scale water purification plant, and granular activated carbon (GAC) preloaded with fulvic acid and/or calcium. The major inorganic material accumulated on BAC was calcium. The amounts of calcium on BAC5.0 and BAC3.5 were 36.6 and 29.7 mg g(-1), respectively. Seventy-one percent of calcium existed as calcium carbonate in both BACs. BAC5.0 had higher amount of accumulated calcium than BAC3.5 even though both BACs have already exhausted for NOM in the influent in 1-year operation, suggesting that calcium carbonate gradually accumulated on BAC even after the 3.5 years of operation. The isotherms of GAC preloaded with fulvic acid and/or calcium clearly indicated that the calcium accumulation on GAC reduced adsorption capacity for simazine. The conclusion also confirmed by significant recovery of adsorption capacity of both BACs by acid-washing to remove accumulated calcium from BACs. The difference of adsorption capacity between BAC3.5 and BAC5.0 was caused not only by the difference of adsorbed NOM but also the difference in the amount of accumulated calcium.