Sources and Transformations of Nitrate from Streams Draining Varying Land Uses: Evidence from Dual Isotope Analysis

Abstract

Knowledge of key sources and biogeochemical processes that affect the transport of nitrate (NO(3)(-)) in streams can inform watershed management strategies for controlling downstream eutrophication. We applied dual isotope analysis of NO(3)(-) to determine the dominant sources and processes that affect NO(3)(-) concentrations in six stream/river watersheds of different land uses. Samples were collected monthly at a range of flow conditions for 15 mo during 2004-05 and analyzed for NO(3)(-) concentrations, delta(15)N(NO3), and delta(18)O(NO3). Samples from two forested watersheds indicated that NO(3)(-) derived from nitrification was dominant at baseflow. A watershed dominated by suburban land use had three delta(18)O(NO3) values greater than +25 per thousand, indicating a large direct contribution of atmospheric NO(3)(-) transported to the stream during some high flows. Two watersheds with large proportions of agricultural land use had many delta(15)N(NO3) values greater than +9 per thousand, suggesting an animal waste source consistent with regional dairy farming practices. These data showed a linear seasonal pattern with a delta(18)O(NO3):delta (15)N(NO3) of 1:2, consistent with seasonally varying denitrification that peaked in late summer to early fall with the warmest temperatures and lowest annual streamflow. The large range of delta (15)N(NO3) values (10 per thousand) indicates that NO(3)(-) supply was likely not limiting the rate of denitrification, consistent with ground water and/or in-stream denitrification. Mixing of two or more distinct sources may have affected the seasonal isotope patterns observed in these two agricultural streams. In a mixed land use watershed of large drainage area, none of the source and process patterns observed in the small streams were evident. These results emphasize that observations at watersheds of a few to a few hundred km(2) may be necessary to adequately quantify the relative roles of various NO(3)(-) transport and process patterns that contribute to streamflow in large basins.