Impacts of long-term acid deposition on soil and water chemistry are of particular concern in the Great Smoky Mountains National Park (GRSM), receiving some of the highest acid deposition rates in the eastern United States and limited by inadequate acid buffering capacity. In the GRSM, the Noland Divide watershed (NDW) has been monitored since 1991 for water chemistries of precipitation, throughfall, soil, and stream. The impacts of long-term acidic deposition on stream water quality in the NDW were investigated through: 1) development of an ion input-output budget; 2) analysis of trends and seasonal patterns for major ions; 3) comparison of net export rates between baseflow and stormflow periods; and 4) characterization of soil chemistry and transport properties for various potential acid deposition scenarios. Between 1991 and 2006, throughfall deposition remained unchanged and consisted of 1,735 eq ha-1 yr-1 of SO42-, 863 eq ha-1 yr-1 of NO3-, and 284 eq ha-1 yr-1 of NH4+. Net retention of sulfate was estimated at 61% being controlled by soil adsorption, and inorganic nitrogen was retained at 32% presumably due to plant uptake. Nitrogen retention increased by 44.30 eq ha-1 yr-1 over the study period. Besides deposition, soil acidity was increased by nitrification and precipitation-driven desorption of previously accumulated sulfate. To neutralize soil acidity, Ca2+, Mg2+ and Na+ were depleted from NDW by 77, 46 and 66 eq ha-1 yr-1, respectively. Due to the continuous addition of acidity, base saturation in soil was reduced to 4% at present. Mobilization of aluminum and other metals (Mn and Zn) may be enhanced by these geochemical processes, potentially causing toxic conditions to fish and other biota in the GRSM streams. Impacts of acidic deposition on streams were confirmed by measured stream pH below 6 and acid neutralizing capacity below 0.01 meq L-1. During stormflows pH and ANC depressions occurred primarily due to increases in sulfate transport, leading to episodic acidification events. This study provides new information on hydrological and biogeochemical processes that regulate stream acidification events in the southern Appalachian region, supporting improved management strategies for GRSM streams.