Contrasting residence times and fluxes of water and sulfate in two small forested watersheds in Virginia, USA.

Watershed mass balances for solutes of atmospheric origin may be complicated by the residence times of water and solutes at various time scales. In two small forested headwater catchments in the Appalachian Mountains of Virginia, USA, mean annual export rates of SO(4)(=) differ by a factor of 2, and seasonal variations in SO(4)(=) concentrations in atmospheric deposition and stream water are out of phase. These features were investigated by comparing (3)H, (35)S, delta(34)S, delta(2)H, delta(18)O, delta(3)He, CFC-12, SF(6), and chemical analyses of open deposition, throughfall, stream water, and spring water. The concentrations of SO(4)(=) and radioactive (35)S were about twice as high in throughfall as in open deposition, but the weighted composite values of (35)S/S (11.1 and 12.1x10(-15)) and delta(34)S (+3.8 and +4.1 per thousand) were similar. In both streams (Shelter Run, Mill Run), (3)H concentrations and delta(34)S values during high flow were similar to those of modern deposition, delta(2)H and delta(18)O values exhibited damped seasonal variations, and (35)S/S ratios (0-3x10(-15)) were low throughout the year, indicating inter-seasonal to inter-annual storage and release of atmospheric SO(4)(=) in both watersheds. In the Mill Run watershed, (3)H concentrations in stream base flow (10-13 TU) were consistent with relatively young groundwater discharge, most delta(34)S values were approximately the same as the modern atmospheric deposition values, and the annual export rate of SO(4)(=) was equal to or slightly greater than the modern deposition rate. In the Shelter Run watershed, (3)H concentrations in stream base flow (1-3 TU) indicate that much of the discharging ground water had been deposited prior to the onset of atmospheric nuclear bomb testing in the 1950s, base flow delta(34)S values (+1.6 per thousand) were significantly lower than the modern deposition values, and the annual export rate of SO(4)(=) was less than the modern deposition rate. Concentrations of (3)H and (35)S in Shelter Run base flow, and of (3)H, (3)He, CFC-12, SF(6), and (35)S in a spring discharging to Shelter Run, all were consistent with a bimodal distribution of discharging ground-water ages with approximately 5-20% less than a few years old and 75-95% more than 40 years old. These results provide evidence for 3 important time-scales of SO(4)(=) transport through the watersheds: (1) short-term (weekly to monthly) storage and release of dry deposition in the forest canopy between precipitation events; (2) mid-term (seasonal to interannual) cycles in net storage in the near-surface environment, and (3) long-term (decadal to centennial) storage in deep ground water that appears to be related to relatively low SO(4)(=) concentrations in spring discharge that dominates Shelter Run base flow. It is possible that the relatively low concentrations and low delta(34)S values of SO(4)(=) in spring discharge and Shelter Run base flow may reflect those of atmospheric deposition before the middle of the 20th century. In addition to storage in soils and biota, variations in ground-water residence times at a wide range of time scales may have important effects on monitoring, modeling, and predicting watershed responses to changing atmospheric deposition in small watersheds.