The upper Alamosa River Basin contains areas that are geochemically altered and have associated secondary sulfide mineralization. Occurring with this sulfide mineralization are copper, gold, and silver deposits that have been mined since the 1870's. Weathering of areas with sulfide mineralization produces runoff with anomalously low pH and high metal concentrations; mining activities exacerbate the condition. Summer rainstorms in the upper Alamosa River Basin produce a characteristic relation between streamflow and pH; streamflow suddenly increases and pH suddenly decreases (commonly by more than 1 pH unit). This report evaluates changes in pH in the upper Alamosa River Basin during July, August, and September 1995, 1996, and 1997 to examine possible adverse environmental effects due to rainstorm runoff. Ninety-three percent of the rainstorms occurring during 1995?97 produced runoff throughout the entire basin. Out of 54 storms, only 3 storms were isolated to the river reach upstream from the streamflow-gaging station Alamosa River above Wightman Fork, and only 1 storm was isolated to the river reach between the streamflow-gaging stations Alamosa River below Jasper and Alamosa River above Terrace Reservoir. Although most rainstorm runoff events occurred throughout the entire basin, pH changes were highest in parts of the basin that receive runoff from hydrothermally altered areas. The three principal altered areas within the basin are the Jasper, Stunner, and Summitville areas. Only limited mining occurred in the Stunner altered area, and yet significant decreases in pH values occur due to runoff from this area. Even after environmental restoration activities are completed at the Summitville Mine, the main stem of the Alamosa River may continue to be adversely affected by runoff from the Stunner and Jasper altered areas. A comparison of measured pH with Federal and State of Colorado water-quality standards and Toxicological Reference Values indicates pH was too low to support aquatic life in many parts of the basin for extended periods of time. Added stresses from sudden decreases in pH due to rainstorm runoff compound the adverse effects. Discharge of effluent from the Summitville Mine impoundment can significantly decrease pH in the Alamosa River downstream to Terrace Reservoir. A release of only 3 cubic feet per second from the impoundment decreased pH by at least 1 standard unit at all downstream sites. Low-flow years may pose a substantial risk to aquatic organisms within and downstream from Terrace Reservoir. During 1996, the basin had a low-flow year, and water storage and pool size of Terrace Reservoir were significantly reduced. The pH of water discharging from Terrace Reservoir was anomalously low during late August and September 1996, possibly due to geochemical interactions between sediment and the water column within the reservoir. In general, an inverse log-log relation exists between pH and the logarithm of dissolved metal concentrations, but the relations generally are not significant enough to confidently predict metal concentrations based upon measured pH values.