Isotopic apportionment of atmospheric and sewage nitrogen sources in two Connecticut rivers.

We used the dual isotope approach to identify sources of nitrate (NO3-) to two mixed land-use watersheds draining to Long Island Sound. In contrastto previous work, we found that sewage effluent NO3- was not consistently enriched in 15N. However, these effluents followed a characteristic denitrification line in delta15N-delta18O space, which could be used as a source signature. We used this signature, together with those of atmospheric deposition and microbial nitrification, to calculate ranges of possible contributions from each of these sources. These estimates are unaffected by any denitrification that may have taken place in soils or streams. Our estimates for atmospheric nitrogen only include unprocessed atmospheric deposition, i.e., NO3-that is not taken up in watershed soils before being delivered to rivers. Using this method, the contribution of atmospheric NO3- could be assessed with good precision and was found to be very low at all our sampling sites during baseflow. During a moderate storm event, atmospheric deposition contributed up to approximately 50% of stream NO3-, depending on the site, with the sites that experienced more stormflow showing a greater contribution of atmospheric NO3-. Our estimates of sewage contribution generally had too large a range to be useful.

Sensitive measurement of NH4+ 15N/14N (delta 15NH4+) at natural abundance levels in fresh and saltwaters.

We report a new method for determining the 15N/14N of NH4+ at natural abundance level in both freshwater and seawater. NH4+ is first quantitatively oxidized to NO2- by hypobromite (BrO-) at pH approximately 12. After the addition of sodium arsenite to consume excess BrO-, yield is verified by colorimetric NO2- determination. NO2- is further reduced to N2O using a 1:1 sodium azide and acetic acid buffer solution using previously established procedures. The product N2O is then analyzed for isotopic composition using a continuous flow purge and cryogenic trap system coupled to an isotope ratio mass spectrometer. Reliable delta 15N values (standard deviation is 0.3 per thousand or better) are obtained over an NH4+ concentration range of 0.5-10 microM using 20 mL volumes of either freshwater or seawater samples. Higher concentration samples are readily diluted to lower concentration. Preexisting NO2- is removed by treatment with sulfanilic acid. There is no interference from any of the nitrogen-containing compounds tested except short-chain aliphatic amino acids (i.e., glycine) which typically are present at very low environmental concentrations. As compared to published methods, our approach is more robust, readily applicable at low concentrations and small sample volumes, and requires less time for preparation and analysis.