18O isotopic separation of stream nitrate sources in mid-Appalachian forested watersheds

The δ18O values of atmospheric nitrate deposition, microbe-produced nitrate, and stream nitrate were measured to determine the dominant source of stream nitrate in 27 mid-Appalachian headwater forested watersheds (12–771 ha) with varying bedrock geologies, land disturbance histories, and stand ages. The 12 monthly composite nitrate δ18O values of wet deposition and throughfall exhibited similar pronounced seasonal trends, with relatively depleted δ18O values during the summer. Wet deposition and throughfall nitrate δ18O values were not significantly different between northern (Leading Ridge, PA) and southern (Fernow, WV) regional sampling sites, indicating that δ18O values were spatially similar across the study area. Atmospheric nitrate δ18O values were significantly greater than microbe-produced nitrate δ18O values, allowing the two sources of stream nitrate to be separated. During four baseflow and three stormflow sampling periods, microbe-produced nitrate was the dominant (>70%) source of nitrate in the study streams. This result does not mean atmospheric nitrogen deposition should be discounted as a source of forested stream nitrate, because atmospheric deposition is the primary external contributor to the long-term soil nitrogen pool that ultimately drives soil nitrate production rates. Stream nitrate δ18O values were greater during stormflow periods compared to baseflow periods, indicating greater contributions of atmospheric nitrate during storm events. Neither microbe-produced nitrate δ18O values from incubated forest soil samples nor stream nitrate δ18O values showed strong relationships with land disturbance history or stand age. However, watersheds dominated by Pottsville/Allegheny bedrock and associated extremely acid soils had greater summer stream nitrate δ18O values than watersheds containing predominantly Catskill/Chemung/Pocono and Mauch Chunk/Greenbrier bedrock. Inhibited microbial nitrate production by low soil pH could account for the greater proportions of atmospheric nitrate deposition in streams draining Pottsville/Allegheny bedrock.