, Volume 25, Issue 6, pp 1077-1087

Comparison of isotope pairing and N2:Ar methods for measuring sediment denitrification—Assumption, modifications, and implications

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Abstract

Denitrification has been measured during the last few years using two different methods in particular: isotope pairing measured on a triple-collector isotopic ratio mass spectrometer and N2:Ar ratios measured on a membrane inlet mass spectrometer (MIMS). This study compares these two techniques in short-term batch experiments. Rates obtained using the original N2∶Ar method were up to 3 to 4 times higher than rates obtained using the isotope pairing technique due to O2 reacting with the N2 during MIMS analysis. Oxygen combines with N2 within the mass spectrometer ion source forming NO+ which reduces the N2 concentration. The decrease in N2 is least at lower O2 concentrations and since oxygen is typically consumed during incubations of sediment cores, the result is often a pseudo-increase in N2 concentration being interpreted as denitrification activity. The magnitude of this ocygen effect may be instrument specific. The reaction of O2 with N2 and the subsequent decrease in N2 was only partly correctly using an O2 correction curve for the relationship between N2 and O2 concentrations. The O2 corrected N2∶Ar denitrification rates were lower, but still did not match the isotope pairing rates and the variability between replicates was much higher. Using a copper reduction column heated to 600°C to remove all of the O2 from the sample before MIMS analysis resulted in comparable rates (slightly lower), and comparable variability between replicates, to the isotope pairing technique. The N2:Ar technique determines the net N2 production as the difference between N2 production by denitrification and N2 consumption by N-fixation, while N-fixation has little effect on the isotope pairing technique which determines a rate very close to the gross N2 production. When the two different techniques were applied on the same sediment, the small difference in rates obtained by the two methods seemed to reflect N-fixation as also supported from measurements of ethylene production in acetylene enriched sediment cores. The N2:Ar and isotope pairing techniques may be combined to provide simultaneous measurements of denitrification and N-fixation. Both techniques have several assumptions that must be met to achieve accurate rates; a number of tests are outlined that can be applied to demonstrate that these assumptions are being meet.