Nitrous oxide formation in the Colne estuary, England: The central role of nitrite

Nitrate and nitrite concentrations in the water and nitrous oxide and nitrite fluxes across the sediment-water interface were measured monthly in the River Colne estuary, England, from December 1996 to March 1998. Water column concentrations of N2O in the Colne were supersaturated with respect to air, indicating that the estuary was a source of N2O for the atmosphere. At the freshwater end of the estuary, nitrous oxide effluxes from the sediment were closely correlated with the nitrite concentrations in the overlying water and with the nitrite influx into the sediment. Increases in N2O production from sediments were about 10 times greater with the addition of nitrite than with the addition of nitrate. Rates of denitrification were stimulated to a larger extent by enhanced nitrite than by nitrate concentrations. At 550 muM nitrite or nitrate (the highest concentration used), the rates of denitrification were 600 mumol N (.) m(-2) (.) h(-1) with nitrite but only 180 mumol N (.) m(-2) (.) h(-1) with nitrate. The ratios of rates of nitrous oxide production and denitrification (N2O/N-2 x 100) were significantly higher with the addition of nitrite (7 to 13% of denitrification) than with nitrate (2 to 4% of denitrification). The results suggested that in addition to anaerobic bacteria, which possess the complete denitrification pathway for N-2 formation in the estuarine sediments, there may be two other groups of bacteria: nitrite denitrifiers, which reduce nitrite to N-2 via N2O, and obligate nitrite-denitrifying bacteria, which reduce nitrite to N2O as the end product. Consideration of free-energy changes during N2O formation led to the conclusion that N2O formation using nitrite as the electron acceptor is favored in the Colne estuary and may be a critical factor regulating the formation of N2O in high-nutrient-load estuaries.