Methane and Nitrous Oxide Temporal and Spatial Variability in Midwestern Streams Containing High Nitrate Concentrations

Interest in greenhouse gases in fluvial environments, e.g. CH4 and N2O, is increasing in relation to atmospheric gas budgets and the relative contribution of streams to drivers of global climate change. Typically these gases are examined individually in environments in which each is expected to be dominant; however their co-occurrence and potential interactions may be important. Spatial and temporal variability of CH4 and N2O concentrations were measured in 2 nitrate-rich (40-1200 μM) streams draining >90% agricultural land use in the Midwestern USA and that differed ~12-fold in flow. Long-term (biweekly), short-term (hourly), and transport-oriented (Lagrangian) sampling approaches were compared. Dissolved gas concentrations exceeded atmospheric equilibrium values up to 700x and 16x, for CH4 and N2O, respectively. Mean concentrations were higher in the larger stream than in the smaller stream. In both streams, CH4 was negatively correlated with flow and nitrate while N2O was positively correlated. N2O was generally constant with transport (21 km) in the small stream, with variation in localized reaches, and increased somewhat in May/June in the larger stream (38 km), but not during September base flow. Base flow transport trends for CH4 were similar to N2O in both streams. In the small stream, substantial diel fluctuations were evident in CH4 concentrations and N2O δ18O values, with more subtle fluctuations in CH4 isotopes (δ2H & δ13C), N2O concentrations, and N2O δ15N values. Seasonal mean total (CH4 + N2O) areal emission rates, expressed as CO2 warming potential equivalents, were similar for the two streams, but the total reach-scale emission rate for the larger stream was about 2x that of the smaller stream (15.4 vs 8.3 kg CO2 km-1 day-1, respectively). The CH4 contribution to this flux was 12-30%, despite the relatively high nitrate and oxygen concentrations in the streams, indicating contributions from groundwater or subsurface sediment reactions.