Abstract. Longitudinal and temporal variations in water chemistry were measured in several low-order, high-elevation streams in the Great Smoky Mountains to evaluate the processes responsible for the acid-base chemistry. The streams ranged in average base flow ANC from -30 to 28 ~eq L -1 and in pH from 4.54 to 6.40. Low-ANC streams had lower base cation concentrations and higher acid anion concentrations than did the high-ANC streams. NO 3 and SO42-were the dominant acid anions. NO 3-was derived from a combination of high leaching of nitrogen from old-growth forests and from high rates of atmospheric deposition. Streamwater SO42-was attributed to atmospheric deposition and an internal bedrock source of sulfur (pyrite). Although dissolved A1 concentrations increased with decreasing pH in the study streams, the concentrations of inorganic monomeric AI did not follow the pattern expected from equilibrium with aluminum trihydroxide or aluminum silicate phases. During storm events, pH and ANC declined by as much as 0.5 units and 15 ~eq L ~, respectively, at the downstream sites. The causes of the episodic acidification were increases in SO42-and DOC.