N tracing models with a Monte Carlo optimization procedure provide new insights on gross N transformations in soils

¹⁵N tracing studies in combination with analyses via process-based models are the current “state-of-the-art” technique to quantify gross nitrogen (N) transformation rates in soils. A crucial component of this technique is the optimization algorithm which primarily decides how many model parameters can simultaneously be estimated. Recently, we published a Markov chain Monte Carlo (MCMC) method which has the potential to simultaneously estimate large number of parameters in ¹⁵N tracing models [Müller et al., 2007. Estimation of parameters in complex ¹⁵N tracing models by Monte Carlo sampling. Soil Biology & Biochemistry 39, 715-726].Here, we present the results of a reanalysis of datasets by Kirkham and Bartholomew [1954. Equations for following nutrient transformations in soil, utilizing tracer data. Soil Science Society of America Proceedings 18, 33-34], Myrold and Tiedje [1986. Simultaneous estimation of several nitrogen cycle rates using ¹⁵N: theory and application. Soil Biology & Biochemistry 18, 559-568] and Watson et al. [2000. Overestimation of gross N transformation rates in grassland soils due to non-uniform exploitation of applied and native pools. Soil Biology & Biochemistry 32, 2019-2030] using the MCMC technique. Analytical solutions such as the ones derived by Kirkham and Bartholomew [1954. Equations for following nutrient transformations in soil, utilizing tracer data. Soil Science Society of America Proceedings 18, 33-34] result in gross rates without uncertainties. We show that the analysis of the same data sets with the MCMC method provides standard deviations for gross N transformations. The standard deviations are further reduced if realistic data uncertainties are considered. Reanalyzing data by Myrold and Tiedje [1986. Simultaneous estimation of several nitrogen cycle rates using ¹⁵N: theory and application. Soil Biology & Biochemistry 18, 559-568] (Capac soil) resulted in a model fit similar to the one of the original analysis but with more precise estimates of gross N transformations. In addition, our analysis showed that small N transformations such as heterotrophic nitrification, which was neglected in the original analysis, could be quantified for this soil. Watson et al. [2000. Overestimation of gross N transformation rates in grassland soils due to non-uniform exploitation of applied and native pools. Soil Biology & Biochemistry 32, 2019-2030] provided evidence of a non-uniform exploitation of applied and native N that led to an overestimation of gross N transformations. Reanalyzing the data (CENIT soil, low N application) with the Müller et al. [2007. Estimation of parameters in complex ¹⁵N tracing models by Monte Carlo sampling. Soil Biology & Biochemistry 39, 715-726] model where oxidation was set to Michaelis-Menten kinetics resulted in a satisfactory fit between modeled and observed data, indicating that the observed artifact by Watson et al. [2000. Overestimation of gross N transformation rates in grassland soils due to non-uniform exploitation of applied and native pools. Soil Biology & Biochemistry 32, 2019-2030] was mainly due to inappropriate kinetic settings. Our study shows that the combination of a MCMC method with ¹⁵N tracing models is able to consider more complex and possibly more realistic models and kinetic settings to estimate gross N transformation rates and thus overcomes restriction of previous ¹⁵N tracing techniques.