Dissolved silica concentrations in western Virginia streams showed a significant bias toward declines (p < 0.0001) over the time period from 1988 to 2003. Streams with the greatest declines were those that had the highest mean dissolved silica concentrations, specific to watersheds underlain by basaltic and granitic bedrock. We examined potential geochemical, hydrological, and biological factors that could account for the observed widespread declines, focusing on six core watersheds where weekly stream chemistry data were available. No relationships were evident between stream water dissolved silica concentrations and pH, a finding supported by the results from a geochemical model applied to the dominant bedrock mineralogy. Along with changes in watershed acidity, changes in precipitation and discharge were also discounted since no significant trends were observed over the study period. Analyses of two longer-term data sets that extend back to 1979 revealed that the initiation of the dissolved silica declines coincided with the timing of a gypsy moth (Lymantria dispar) defoliation event. We develop a conceptual model centered on benthic diatoms, which are found within each of the six core watersheds but in greater abundance in the more silica-rich streams. Gypsy moth defoliation led to greater sunlight penetration and enhanced nitrate concentrations in the streams, which could have spurred population growth and silica uptake. The model can explain why the observed declines are primarily driven by decreased concentrations during low-flow conditions. This study illustrates lasting effects of disturbance on watershed biogeochemistry, in this case causing decadal-scale variability in stream water dissolved silica concentrations.