No abstract

Nonpoint source nitrogen (N) pollution is a leading contributor to U.S. water quality impairments. We combined watershed N mass balances and stable isotopes to investigate fate and transport of nonpoint N in forest, agricultural, and urbanized watersheds at the Baltimore Long-Term Ecological Research site. Annual N retention was 55%, 68%, and 82% for agricultural, suburban, and forest watersheds, respectively. Analysis of δ(15)N-NO(3)(-), and δ(18)O-NO(3)(-) indicated wastewater was an important nitrate source in urbanized streams during baseflow. Negative correlations between δ(15)N-NO(3)(-) and δ(18)O-NO(3)(-) in urban watersheds indicated mixing between atmospheric deposition and wastewater, and N source contributions changed with storm magnitude (atmospheric sources contributed ∼50% at peak storm N loads). Positive correlations between δ(15)N-NO(3)(-) and δ(18)O-NO(3)(-) in watersheds suggested denitrification was removing septic system and agriculturally derived N, but N from belowground leaking sewers was less susceptible to denitrification. N transformations were also observed in a storm drain (no natural drainage network) potentially due to organic carbon inputs. Overall, nonpoint sources such as atmospheric deposition, wastewater, and fertilizer showed different susceptibility to watershed N export. There were large changes in nitrate sources as a function of runoff, and anticipating source changes in response to climate and storms will be critical for managing nonpoint N pollution.

Despite the potential use of δ(15)N as a tracer of NO(x) source contributions, prior documentation of δ(15)N of various NO(x) emission sources is exceedingly limited. This manuscript presents the first measurements of the nitrogen isotopic composition of NO(x) (δ(15)N-NO(x)) emitted from coal-fired power plants in the U.S. at typical operating conditions with and without the presence of selective catalytic reduction (SCR) and selective noncatalytic reduction (SNCR) technology. To accomplish this, a novel method for collection and isotopic analysis of coal-fired stack NO(x) emission samples was developed based on modifications of a historic U.S. EPA stack sampling method. At the power plants included in this study, large differences exist in the isotopic composition of NO(x) emitted with and without SCRs and SNCRs; further the isotopic composition of power plant NO(x) is higher than that of other measured NO(x) emission sources confirming its use as an environmental tracer. These findings indicate that gradual implementation of SCRs at power plants will result in an industry-wide increase in δ(15)N values of NO(x) and NO(y) oxidation products from this emission source.

Global inputs of NO(x) are dominated by fossil fuel combustion from both stationary and vehicular sources and far exceed natural NO(x) sources. However, elucidating NO(x) sources to any given location remains a difficult challenge, despite the need for this information to develop sound regulatory and mitigation strategies. We present results from a regional-scale study of nitrogen isotopes (delta15N) in wet nitrate deposition across 33 sites in the midwestern and northeastern U.S. We demonstrate that spatial variations in delta15N are strongly correlated with NO(x) emissions from surrounding stationary sources and additionally that delta15N is more strongly correlated with surrounding stationary source NO(x) emissions than pH, SO4(2-), or NO3- concentrations. Although emission inventories indicate that vehicle emissions are the dominant NO(x) source in the eastern U.S., our results suggest that wet NO3- deposition at sites in this study is strongly associated with NO(x) emissions from stationary sources. This suggests that large areas of the landscape potentially receive atmospheric NO(y) deposition inputs in excess of what one would infer from existing monitoring data alone. Moreover, we determined that spatial patterns in delta15N values are a robust indicator of stationary NO(x) contributions to wet NO3- deposition and hence a valuable complement to existing tools for assessing relationships between NO3- deposition, regional emission inventories, and for evaluating progress toward NO(x) reduction goals.

[1] Dry deposition is a major component of total atmospheric nitrogen deposition and thus an important source of bioavailable nitrogen to ecosystems. However, relative to wet deposition, less is known regarding the sources and spatial variability of dry deposition. This is in part due to difficulty in measuring dry deposition and associated deposition velocities. Passive sampling techniques offer potential for improving our understanding of the spatial distribution and sources of gaseous and aerosol N species, referred to here as dry deposition. We report dual nitrate isotopic composition ( O values between actively and passively collected samples; the causes for this offset warrant further investigation. Nonetheless, passive sample collection represents a significant cost savings over active sampling techniques and could allow a more extensive understanding of patterns of dry deposition and associated insights to nitrogen sources across landscapes.

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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.

Increased deposition of reactive atmospheric N has resulted in the nitrogen saturation of many forested catchments worldwide. Isotope-based studies from multiple forest sites report low proportions (mean 5 10%) of unprocessed atmospheric nitrate in streams during baseflow, regardless of N deposition or nitrate export rates. Given similar proportions of atmospheric nitrate in baseflow across a variety of sites and forest types, it is important to address the postdepositional drivers and processes that affect atmospheric nitrate transport and fate within catchments. In a meta-analysis of stable isotope-based studies, we examined the influence of methodological, biological, and hydrologic drivers on the export of atmospheric nitrate from forests. The d values tended to increase with increasing baseflow discharge at all sites examined. To explain these differences, we present a conceptual model of hydrologic flowpath characteristics (e.g., saturation overland flow versus subsurface stormflow) that considers the influence of topography on landscape-stream hydrologic connectivity and delivery of unprocessed atmospheric nitrate to streams. Methodological biases resulting from differences in sampling frequency and stable isotope analytical techniques may further influence the perceived degree of unprocessed atmospheric nitrate export. Synthesis of results from numerous isotope-based studies shows that small proportions of unprocessed atmospheric nitrate are common in baseflow. However, hydrologic, topographic, and methodological factors are important drivers of actual or perceived elevated contributions of unprocessed atmospheric nitrate to streams.