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This study aims to determine the sources of nitrate in precipitation, groundwater, and surface water in an alpine watershed. Isotope analysis of nitrogen and oxygen is used to track the fluxes and transformations of nitrogen through hydrologic pathways. The study also links plot-scale ecosystem measurements to catchment-scale flux measurements.
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Pathways for nitrate release from an alpine watershed: Determination using 15 N and 18 O Donald H. Campbell Carol Kendall, Cecily C. Y. Chang, Steven R. Silva Kathy A. Tonnessen
Study: Objective • Determine sources of nitrate in precipitation, groundwater, and surface water • Follow the fluxes and transformations of nitrogen through the hydrologic pathways • Link plot-scale measurements of ecosystem processes to catchment-scale flux measurements
15N & 18O Isotopes • 15N is useful to determine nitrate concentration in areas affected by agriculture, but not in undisturbed watersheds - 15N values for atmospheric deposition and microbial processes have similar 15N (NO3) values that over lap • 18O(NO3) can be used to help separate atmospheric sources of nitrate from microbial
Nitrate Double-Isotope Technique • Mircobial nitrification derives two oxygen’s from water molecules and one from atmospheric • Knowing this, and 18O of water and O2, you can calculate 18Oof microbial nitrate 18O(NO3)= 2/3 18O(H20) + 1/3 18O(O2) • Using this model and the normal range of values for 18O(H2O) (-25 to+ 4%) and 18O of soil O2 gas (about +23%), then you get a range of -10 to +10% 18O(NO3)
Nitrate Double-Isotope Technique • Model is built on four assumptions, • Oxygen to water proportions are the same in soils as they are in lab cultures • No fractionation • 18O of water used by microbes is the same water that is being sampled • 18O of O2 used by the microbes is the same as the atmospheric O2
Nitrate Double-Isotope Technique • Problem is that under natural conditions some of the assumptions may be violated • Several studies have shown higher 18O(NO3) values by as much as 5% greater than the theoretically calculated value of +10% • Possibly due to fractionation of O2 during respiration and a fluctuating ratio of oxygens derived from water, versus those derived from O2 gas • For the study a value of 0 to +15% was used
Site /Sampling • In Loch Vale watershed, Rocky Mtn. National Park • Two main sub-basins, Icy Brook and Andrews Creek were sampled • Two springs emerging from Talus deposits were also sampled
Results: Snowpack • Earliest snowmelt samples had isotopic nitrate compositions similar to the winter snowpack, followed by decreasing O18 and N15 values • 15N decreased from +55 to 65% in winter down to +40% for spring • 18O values changed from +2.2% in winter to +.5% for spring
Results: Stream Water • Both streams Icy Brook and Andrews Creek had 15N(NO3) values from -1 to +2% and 18O(NO3) values that ranged from +10 to +25% • A sample collected early April 1996, from Andrews Creek, had nearly identical 18O(NO3) values compared to the atmospheric deposition values *A similar event was observed during early snowmelt in 1994
Results: Talus Springs • Nitrate concentrations observed ranged from 24 to 64 ueq/L and 18O(NO3) values were between +10 to +27% • The talus springs had high nitrate concentrations and a seasonal pattern in 18O(NO3) that was observed in the streams • Important sources of nitrate later in the summer
Seasonal Pattern • Nitrate Concentrations in the stream water, peaked in late May, decreased throughout the summer, and then started to rise again in the Fall • The seasonal variation is believed to be caused from differences in storm patterns and varying sources of nitrogen oxide in the front range • Despite seasonal variation values, from 1995-1997 were constant for 18O and 15N values of nitrate, with only a 1% difference in the range for 15N, and 5% for 18O.
Fluxes and Residence Time • A relatively small seasonal variance in 18O(H20) was seen, suggesting a long residence time and large reservoir of water • Residence time was thought to be almost a year for Andrews Creek, allowing
Results • 18O(NO3) values for Talus springs and streams indicated that most of the nitrate had undergone nitrification and was not directly from atmospheric deposition • Despite the apparent lack of soil, microbial cycling controls the supply of nitrate in the Loch Vale watershed • The fluxes of nitrate being exported from the system are a function of the hydrologic variables (flow paths, residence time, and reservoir sizes) • Both biogeochemical and hydrologic processes control the export of nitrate in alpine streams and springs.