Nitrogen and oxygen isotope enrichment factors of nitrate at different denitrification rates in an agricultural soil

ABSTRACT

Quantitative evaluation of denitrification by the dual isotope approach, which measures the stable isotope ratios of nitrogen (δ¹⁵N) and oxygen (δ¹⁸O) in nitrate, has been hampered by the wide range of values reported for the ratio of enrichment factors for ¹⁵N and ¹⁸O (¹⁵ε and ¹⁸ε, respectively) during denitrification. The objectives of this study were to determine ¹⁵ε and ¹⁸ε values at different denitrification rates under controlled conditions, and to infer possible mechanisms by which the ¹⁸ε/¹⁵ε ratio is influenced under different conditions. Column experiments were conducted at 25, 15, and 10°C, which enabled determination of ¹⁵ε and ¹⁸ε at different denitrification rates, in the absence of nitrate replenishment from ammonium oxidation and other sources. The values of ¹⁵ε and ¹⁸ε ranged from ?11.8 to ?14.9‰ and from ?8.4 to ?15.9‰, respectively, with ¹⁵ε less sensitive to changes in the denitrification rates. The resultant ¹⁸ε/¹⁵ε ratio, ranging from 0.70 to 1.17, was close to the values reported for sediment incubations, and larger than those for groundwater systems. These results are consistent with the explanations that ¹⁸ε/¹⁵ε value itself is close to unity during denitrification, and that at smaller denitrification rates, concurrent reactions including re-oxidation of nitrite to nitrate lead to smaller apparent fractionation of ¹⁸O and smaller ¹⁸ε/¹⁵ε ratios. This suggests that while linear relationships between δ¹⁸O and δ¹⁵N give a strong evidence of denitrification, apparent ¹⁸ε/¹⁵ε values are site specific and depend on the ambient conditions. In evaluating denitrification in such systems, we suggest the use of ¹⁵ε in preference to ¹⁸ε because ¹⁵ε is less sensitive to denitrification rates.