Groundwater N2O emission factors of nitrate-contaminated aquifers as derived from denitrification progress and N2O accumulation

Abstract

We investigated the dynamics of denitrification and nitrous oxide (N2O) accumulation in 4 nitrate (NO3-) contaminated denitrifying sand and gravel aquifers of northern Germany (Fuhrberg, Sulingen, Thulsfelde and Gottingen) to quantify their potential N2O emission and to evaluate existing concepts of N2O emission factors. Excess N-2 - N-2 produced by denitrification - was determined by using the argon (Ar) concentration in groundwater as a natural inert tracer, assuming that this noble gas functions as a stable component and does not change during denitrification. Furthermore, initial NO3- concentrations (NO3- that enters the groundwater) were derived from excess N-2 and actual NO3- concentrations in groundwater in order to determine potential indirect N2O emissions as a function of the N input. Median concentrations of N2O and excess N-2 ranged from 3 to 89 mu g N L-1 and from 3 to 10 mg N L-1, respectively. Reaction progress (RP) of denitrification was determined as the ratio between products (N2O-N + excess N-2) and starting material (initial NO3- concentration) of the process, characterizing the different stages of denitrification. N2O concentrations were lowest at RP close to 0 and RP close to 1 but relatively high at a RP between 0.2 and 0.6. For the first time, we report groundwater N2O emission factors consisting of the ratio between N2O-N and initial NO3--N concentrations (EF1). In addition, we determined a groundwater emission factor (EF2) using a previous concept consisting of the ratio between N2O-N and actual NO3--N concentrations. Depending on RP, EF(1) resulted in smaller values compared to EF(2), demonstrating (i) the relevance of NO3- consumption and consequently (ii) the need to take initial NO3--N concentrations into account. In general, both evaluated emission factors were highly variable within and among the aquifers. The site medians ranged between 0.00043-0.00438 for EF(1) and 0.00092-0.01801 for EF(2), respectively. For the aquifers of Fuhrberg and Sulingen, we found EF(1) median values which are close to the 2006 IPCC default value of 0.0025. In contrast, we determined significant lower EF values for the aquifers of Thulsfelde and Gottingen. Summing the results up, our study supports the substantial downward revision of the IPCC default EF5-g from 0.015 (1997) to 0.0025 (2006).