Nitrous oxide emission from denitrification in stream and river networks

Abstract

Nitrous oxide (N 2 O) is a potent greenhouse gas that contributes to climate change and stratospheric ozone destruction. Anthropogenic nitrogen (N) loading to river networks is a potentially important source of N 2 O via microbial denitrification that converts N to N 2 O and dinitrogen (N 2 ). The fraction of denitrified N that escapes as N 2 O rather than N 2 (i.e., the N 2 O yield) is an important determinant of how much N 2 O is produced by river networks, but little is known about the N 2 O yield in flowing waters. Here, we present the results of whole-stream 15 N-tracer additions conducted in 72 headwater streams draining multiple land-use types across the United States. We found that stream denitrification produces N 2 O at rates that increase with stream water nitrate (NO 3 − ) concentrations, but that <1% of denitrified N is converted to N 2 O. Unlike some previous studies, we found no relationship between the N 2 O yield and stream water NO 3 − . We suggest that increased stream NO 3 − loading stimulates denitrification and concomitant N 2 O production, but does not increase the N 2 O yield. In our study, most streams were sources of N 2 O to the atmosphere and the highest emission rates were observed in streams draining urban basins. Using a global river network model, we estimate that microbial N transformations (e.g., denitrification and nitrification) convert at least 0.68 Tg·y −1 of anthropogenic N inputs to N 2 O in river networks, equivalent to 10% of the global anthropogenic N 2 O emission rate. This estimate of stream and river N 2 O emissions is three times greater than estimated by the Intergovernmental Panel on Climate Change. Humans have more than doubled the availability of fixed nitrogen (N) in the biosphere, particularly through the production of N fertilizers and the cultivation of N-fixing crops ( 1 ). Increasing N availability is producing unintended environmental consequences including enhanced emissions of nitrous oxide (N 2 O), a potent greenhouse gas ( 2 ) and an important cause of stratospheric ozone destruction ( 3 ). The Intergovernmental Panel on Climate Change (IPCC) estimates that the microbial conversion of agriculturally derived N to N 2 O in soils and aquatic ecosystems is the largest source of anthropogenic N 2 O to the atmosphere ( 2 ). The production of N 2 O in agricultural soils has been the focus of intense investigation (i.e., >1,000 published studies) and is a relatively well constrained component of the N 2 O budget ( 4 ). However, emissions of anthropogenic N 2 O from streams, rivers, and estuaries have received much less attention and remain a major source of uncertainty in the global anthropogenic N 2 O budget. Microbial denitrification is a large source of N 2 O emissions in terrestrial and aquatic ecosystems. Most microbial denitrification is a form of anaerobic respiration in which nitrate (NO 3 − , the dominant form of inorganic N) is converted to dinitrogen (N 2 ) and N 2 O gases ( 5 ). The proportion of denitrified NO 3 − that is converted to N 2 O rather than N 2 (hereafter referred to as the N 2 O yield and expressed as the mole ratio) partially controls how much N 2 O is produced via denitrification ( 6 ), but few studies provide information on the N 2 O yield in streams and rivers because of the difficulty of measuring N 2 and N 2 O production in these systems. Here we report rates of N 2 and N 2 O production via denitrification measured using whole-stream 15 NO 3 − -tracer experiments in 72 headwater streams draining different land-use types across the United States. This project, known as the second Lotic Intersite Nitrogen eXperiment (LINX II), provides unique whole-system measurements of the N 2 O yield in streams. Although N 2 O emission rates have been reported for streams and rivers ( 7 , 8 ), the N 2 O yield has been studied mostly in lentic freshwater and marine ecosystems, where it generally ranges between 0.1 and 1.0%, although yields as high as 6% have been observed ( 9 ). These N 2 O yields are low compared with observations in soils (0–100%) ( 10 ), which may be a result of the relatively lower oxygen (O 2 ) availability in the sediments of lakes and estuaries. However, dissolved O 2 in headwater streams is commonly near atmospheric equilibrium and benthic algal biofilms can produce O 2 at the sediment–water interface, resulting in strong redox gradients more akin to those in partially wetted soils. Thus, streams may have variable and often high N 2 O yields, similar to those in soils ( 11 ). The N 2 O yield in headwater streams is of particular interest because much of the NO 3 − input to rivers is derived from groundwater upwelling into headwater streams. Furthermore, headwater streams compose the majority of stream length within a drainage network and have high ratios of bioreactive benthic surface area to water volume ( 12 ).