Dual isotope ratio normalization of nitrous oxide by bacterial denitrification of USGS reference materials

Abstract

We measured the δ values of N2O using gas chromatography isotope ratio mass spectrometry with a preconcentrator (precon-GC-IRMS). The instrumental precision of the mass spectrometer was restricted to below the shot noise limit, which agreed with the theoretical and experimental results of 0.02‰ (δ15N) and 0.04‰ (δ18O), respectively. The precision of the measured δ values was significantly improved by the temperature regulation protocol of the LN2 preconcentrator, which was monitored by various temperature sensors placed along the U-trap. The reproducibility of the He-diluted N2O gas measurements resulted in 0.063‰ (δ15N) and 0.075‰ (δ18O) due to additional sources of uncertainty in the vials used for autosampling and in the general preconcentration process. Multipoint normalization of the dual δ values of the measured N2O samples was conducted using United States Geological Survey reference materials denitrified by Pseudomonas aureofaciens. Kaiser's ion correction method, based on International Atomic Energy Agency parameters, exhibited low bias for the atomic isotope ratio reduction of the nitrate reference material, for which the oxygen anomaly was considerably high. Dedicated corrections for net isotope fractionation and water exchange were important in improving uncertainties in the procedure for normalizing the oxygen isotope ratio. Blank measurements for correcting biases in isotope ratios caused by pre-dissolved nitrate and nitrite ions in the water solvent led to further improvements, i.e. beyond unevenly controlled net isotope fractionation, throughout the bacterial denitrification process. The uncertainty evaluation revealed that three-point normalization can significantly improve the normalization accuracy compared with two-point normalization. In addition, an alternative strategy was suggested for assigning δ18O using a CO2 lab tank, allowing its use as a reference material for N2O gas tanks.