Urban development has degraded numerous headwater streams. Objectives of this study are: (1) to characterize variation in baseflow hydrochemistry in headwater streams of the South River Watershed (Atlanta, GA, USA) and relate it to differences in land use and other characteristics, as well as to (2) examine solute dynamics during storm events. Results suggest that land use on the watershed scale has a significant influence on mean baseflow nitrate concentration at a given site, with antecedent precipitation also playing a role. Additionally, we collected samples throughout storm events at three USGS stream gage sites. Water chemistry data was paired with USGS discharge and specific conductivity measurements to create concentration-discharge plots. Results from both baseflow and stormflow sampling suggest that, within this watershed, maximum solute concentrations at any location are generally observed at baseflow. As such, this is a source-limited system where groundwater also represents the highest-concentration component of storm flow.