Hydrochemical sampling of South Pennine (UK) headwater streams draining eroded upland peatlands demonstrates these systems are nitrogen saturated, with significant leaching of dissolved inorganic nitrogen (DIN), particularly ammonium, during both stormflow and baseflow conditions. DIN leaching at sub-catchment scale is controlled by geomorphological context; in catchments with low gully densities ammonium leaching dominates whereas highly gullied catchments leach ammonium and nitrate since lower water tables and increased aeration encourages nitrification. Stormflow flux calculations indicate that: approximately equivalent amounts of nitrate are deposited and exported; ammonium export significantly exceeds atmospheric inputs. This suggests two ammonium sources: high atmospheric loadings; and mineralisation of organic nitrogen stored in peat. Downstream trends indicate rapid transformation of leached ammonium into nitrate. It is important that low-order headwater streams are adequately considered when assessing impacts of atmospheric loads on the hydrochemistry of stream networks, especially with respect to erosion, climate change and reduced precipitation. © 2011 Elsevier Ltd. All rights reserved.