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Nitrogen pollution and global eutrophication are predicted to increase nitrous oxide (N 2 O) emissions from freshwater ecosystems. Surface waters within agricultural landscapes experience the full impact of these pressures and can contribute substantially to total landscape N 2 O emissions. However, N 2 O measurements to date have focused on flowing waters. Small artificial waterbodies remain greatly understudied in the context of agricultural N 2 O emissions. This study provides a regional analysis of N 2 O measurements in small (<0.01 km 2 ) artificial reservoirs, of which an estimated 16 million exist globally. We show that 67% of reservoirs were N 2 O sinks (-12 to -2 μmol N 2 O⋅m -2 ⋅d -1 ) in Canada's largest agricultural area, despite their highly eutrophic status [99 ± 289 µg⋅L -1 chlorophyll-a (Chl- a )]. Generalized additive models indicated that in situ N 2 O concentrations were strongly and nonlinearly related to stratification strength and dissolved inorganic nitrogen content, with the lowest N 2 O levels under conditions of strong water column stability and high algal biomass. Predicted fluxes from previously published models based on lakes, reservoirs, and agricultural waters overestimated measured fluxes on average by 7- to 33-fold, challenging the widely held view that eutrophic N-enriched waters are sources of N 2 O., Competing Interests: The authors declare no conflict of interest.

Freshwater lakes are known to release carbon dioxide (CO(2)) and methane (CH(4)) to the atmosphere; however, the importance of lakes in global nitrous oxide (N(2)O) budgets is not yet known. Further, despite the abundance of small lakes on the landscape, neither emissions of these gases nor their drivers are well described. Dissolved concentrations of CO(2), CH(4) and N(2)O greenhouse gases were related to water chemistry, hydrology and catchment characteristics in order to identify factors controlling gas concentrations for 121 small Irish headwater lakes (median area: 2.0ha) in relatively undisturbed catchments; lake-atmosphere gas fluxes were also calculated. The majority of lakes were supersaturated (relative to the atmosphere) with CO(2) and N(2)O while CH(4) was above saturation in all lakes. Dissolved gas concentrations were correlated with land cover (rock, forest and grassland), deuterium excess (an indicator of hydrologic character) and lake organic carbon concentrations, although dissolved CO(2) exhibited few significant relationships. Principal components analysis indicated that higher levels of CH(4) and N(2)O supersaturation were exhibited under different conditions. Methane supersaturation was highest in low elevation catchments with an evaporative hydrologic character and high organic carbon concentrations. In contrast, lakes characteristic of N(2)O supersaturation were low in carbon and located in more rapidly flushed higher elevation catchments. Estimated fluxes of CO(2), CH(4) and N(2)O to the atmosphere averaged 14, 0.36 and 1.3×10(-3)mmolm(-2)d(-1), respectively., (Copyright © 2011 Elsevier B.V. All rights reserved.)

Global models have indicated agriculturally impacted rivers and streams may be important sources of the greenhouse gas nitrous oxide (N(2)O). However, there is significant uncertainty in N(2)O budgets. Isotopic characterization can be used to help constrain N(2)O budgets. We present the first published measurements of the isotopic character of N(2)O emitted from low (2-4) order streams. Isotopic character of N(2)O varied seasonally, among streams, and over diel periods. On an annual basis, δ(18)O of emitted N(2)O (+47.4 to +51.4‰; relative to VSMOW) was higher than previously reported for larger rivers, but δ(15)N of emitted N(2)O (-16.2 to +2.4‰ among streams; relative to atmospheric N(2)) was similar to that of past studies. On an annual basis, all streams emitted N(2)O with lower δ(15)N than tropospheric N(2)O. Given these streams have elevated nitrate concentrations which are associated with enhanced N(2)O fluxes, this supports the hypothesis that streams are contributing to the accumulation of (15)N-depleted N(2)O in the troposphere.

Summary 1. Diel variation in metabolism contributes to variation in oxygen (O2) concentrations in streams. This variation in O2 and other parameters (e.g. pH) can in turn affect the rates of microbial nitrogen (N) processing, concentrations of nitrogenous solutes and production of the greenhouse gas nitrous oxide (N2O). We investigated diel variability in emissions of N2O and the magnitude of short-term variability in N solutes across 10 streams. 2. Nitrous oxide fluxes varied on average 2.3-fold over diel cycles. Concentrations would be underestimated by sampling around noon, but N2O fluxes would not show a consistent bias. Time-weighted mean daily N2O flux was strongly related to nitrate concentration ( r2 = 0.58). Diel patterns in N2O and dissolved N species were often complex (rather than simple sinusoidal curves), probably reflecting complex underlying processes. 3. Reliance on samples obtained around noon would overestimate daily mean nitrate concentrations by 5% and underestimate ammonium by 32% (average bias across all streams and dates). 4. Dissolved organic N did not show consistent day-night variation. However, the magnitude of diel variability was similar to that observed for dissolved inorganic N. Organic and inorganic N concentrations were often similar. Both appear to be dynamic components of stream N budgets. 5. The Intergovernmental Panel on Climate Change (IPCC) relies upon an emission factor to estimate indirect agricultural N2O emissions from streams and ground water. The measured emission factor (defined as the ratio of concentrations of N2O-N to -N) was typically below the recently revised IPCC default figure. Measured values varied on average 1.8-fold over approximately 24-h periods and were slightly higher at night than by day. The emission factor was actually highest in streams that were net sinks for N2O, highlighting a conceptual problem in the current IPCC method. 6. Typical sampling programmes rely on daytime-only sampling, which might cause bias in results. In our study streams, the bias was generally small. Diel variation in nitrate concentrations was related to mean temperature; variation in ammonium and N2O concentrations was greatest at low concentrations of nitrite and ammonium. [ABSTRACT FROM AUTHOR]