Effect of chloride on the chemical conversion of nitrate to nitrous oxide for δ15N analysis
Limnol. Oceanogr. Methods 7:545-552 (2009) | DOI: 10.4319/lom.2009.7.545
ABSTRACT: We investigate the influence of chloride concentration on the performance of the chemical reduction method for measurement of the nitrogen isotopic ratio (δ15N) in NO3 in natural waters (McIlvin and Altabet, 2005). In this method, NO3 is first reduced to NO2 using activated cadmium metal, with further reduction to N2O using sodium azide in an acetic acid buffer. N2O is introduced into an isotope ratio mass spectrometer (IRMS) for isotopic measurement. Previously, it was recognized that the presence of halides was necessary for the speed and efficiency of the second step but not thought to be important for the first step. Whereas quantitative Cd reduction of NO3 to NO2 had been noted for seawater samples, here we report, for freshwater and low-salinity (S < 30) samples, a variable conversion efficiency (both under- and overreduction were observed) and significant variation in δ15N determination. Addition of 5 M NaCl to all samples resulted in rapid (<4 h) and quantitative (>99%) reduction of NO3 to NO2 as well as stable δ15N values that closely matched expected values for standards (within 0.3‰ of standard value). The positive effect of NaCl is likely due to a decrease in free Cd2+ produced over the course of the reaction due to formation of CdCl2.