Abstract:
Ammonium is a key dissolved inorganic nitrogen (DIN) in the biogeochemical cycle of nitrogen in the ocean. Depending on the environment, the
15N natural abundance (δ
15N
air ) of NH
4+ can provide insights into N sources and mechanisms of N transformations in terrestrial ecosystems. A variety of methods have been developed for δ
15N
air determination for NH
4+ during the past several decades, such as the steam distillation method, ammonia diffusion method, ion exchange method and chemical conversion method. The former three methods are not unsuitable for low NH
4+ concentration in seawater samples. In this study, a pretreatment method was developed for determination of nitrogen isotopic composition in ammonium based on the chemical method by hypobromite oxidation combined with sodium azide. To determine the reagent blank source and the effection on the yield rate and the value of δ
15N
air, the appropriate reagent additions, NH
4+ concentration were analyzed. There is no interference from any of the nitrogen-containing compounds tested. Higher concentration samples are readily diluted to lower concentration or taken a small volume. When the NH
4+ concentration ranged from 5 to 50 μmol/L, the yield rate of ammonium converting to N
2O was greater than 92%. And the calibration curves of ammonium isotopic standards with different abundances showed a good linearity The slope was 0.465 which was close to the theoretical values of 0.5. The standard deviation of δ
15N
air measurements was 0.35‰ (
n=5), and the difference between the measured value and the reference value was 0.26‰. This method was used to determination of the nitrogen isotopic composition of dissolved ammonium in seawater, and δ
15N
air (NH
4+) value were between 11.46‰ to 22.31‰ . The standard deviation were between 0.20‰ to 0.62‰ (
n=5). This method meet the requirements of ammonium nitrogen isotope analysis in seawater.