Predicting the denitrification capacity of sandy aquifers from in situ measurements using push-pull ¹⁵N tracer tests

Knowledge about the spatial variability of in situ denitrification rates (Dr(in situ)) and their relation to the denitrification capacity in nitrate-contaminated aquifers is crucial to predict the development of groundwater quality. Therefore, 28 push-pull 15N tracer tests for the measurement of in situ denitrification rates were conducted in two sandy Pleistocene aquifers in Northern Germany. The 15N analysis of denitrification derived 15N labelled N2 and N2O dissolved in water samples collected during the push-pull 15N tracer tests was performed by isotope ratio mass spectrometry (IRMS) in the lab and additionally for some tracer tests online in the field with a quadrupole membrane inlet mass spectrometer (MIMS), in order to test the feasibility of on-site real-time 15N analysis. Aquifer material from the same locations and depths as the push-pull injection points was incubated and the initial and cumulative denitrification after one year of incubation (Dcum(365)) as well as the stock of reduced compounds (SRC) was compared with in situ measurements of denitrification. This was done to derive transfer functions suitable to predict Dcum(365) and SRC from Dr(in situ). Dr(in situ) ranged from 0 to 51.5 μg N kg−1 d−1. Denitrification rates derived from on-site isotope analysis using membrane-inlet mass spectrometry satisfactorily coincided with laboratory analysis by conventional isotope ratio mass spectrometry, thus proving the feasibility of in situ analysis. Dr(in situ) was significantly higher in the sulphidic zone of both aquifers compared to the zone of non-sulphidic aquifer material. Overall, regressions between the Dcum(365) and SRC of the tested aquifer material with Dr(in situ) exhibited only a modest linear correlation for the full data set. But the predictability of Dcum(365) and SRC from Dr(in situ) data clearly increased for aquifer samples from the zone of NO3−-bearing groundwater. In the NO3−-free aquifer zone a lag phase of denitrification after NO3− injections was observed, which confounded the relationship between reactive compounds and in situ denitrification activity. This finding was attributed to adaptation processes in the microbial community after NO3− injections. Exemplarily, it was demonstrated that the microbial community in the NO3−-free zone close below the NO3−-bearing zone can be adapted to denitrification by amending wells with NO3−-injections for an extended period. In situ denitrification rates were 30 to 65% higher after pre-conditioning with NO3−. Results from this study suggest that such pre-conditioning is crucial for the measurement of Dr(in situ) in deeper aquifer material from the NO3−-free groundwater zone and thus for the prediction of Dcum(365) and SRC from Dr(in situ).