The Southern Blue Ridge Province, which encompasses parts of northern Georgia, eastern Tennessee, and western North Carolina, has been predicted to be sensitive to impacts from acidic deposition, owing to the chemical composition of the bedrock geology and soils. This study confirms the predicted potential sensitivity, quantifies the level of total alkalinity and describes the chemical characteristics of 30 headwater streams of this area. Water chemistry was measured five times between April 1983 and June 1984 at first and third order reaches of each stream during baseflow conditions. Sensitivity based on total alkalinity and the Calcite Saturation Index indicates that the headwater streams of the Province are vulnerable to acidification. Total alkalinity and p11 were generally higher in third order reaches (mean, 72 ?eq/? and 6.7) than in first order reaches (64 ?eq/? and 6.4). Ionic concentrations were low, averaging 310 and 340 ?eq/? in first and third order reaches, respectively. A single sampling appears adequate for evaluating sensitivity based on total alkalinity, but large temporal variability requires multiple sampling for the detection of changes in pH and alkalinity over time. Monitoring of stream water should continue in order to detect any subtle effects of acidic deposition on these unique resource systems.