The rising atmospheric CO 2 concentrations have effects on the worldwide ecosystems such as an increase in biomass production as well as changing soil processes and conditions. Since this affects the ecosystem's net balance of greenhouse gas emissions, reliable projections about the CO 2 impact are required. Deterministic models can capture the interrelated biological, hydrological, and biogeochemical processes under changing CO 2 concentrations if long-term observations for model testing are provided. We used 13 years of data on above-ground biomass production, soil moisture, and emissions of CO 2 and N 2 O from the Free Air Carbon dioxide Enrichment (FACE) grassland experiment in Giessen, Germany. Then, the LandscapeDNDC ecosystem model was calibrated with data measured under current CO 2 concentrations and validated under elevated CO 2 . Depending on the hydrological conditions, different CO 2 effects were observed and captured well for all ecosystem variables but N 2 O emissions. Confidence intervals of ensemble simulations covered up to 96% of measured biomass and CO 2 emission values, while soil water content was well simulated in terms of annual cycle and location-specific CO 2 effects. N 2 O emissions under elevated CO 2 could not be reproduced, presumably due to a rarely considered mineralization process of organic nitrogen, which is not yet included in LandscapeDNDC.Agronomy 2020, 10, 50 2 of 17 climatic changes such as rising temperatures, shifting precipitation patterns, and unpredictable extreme events [2]. To assess the interaction of elevated CO 2 with the carbon (C) cycle outside of controlled laboratory environments, Free Air Carbon dioxide Enrichment (FACE) experiments were established to observe the reaction of whole ecosystems to enhanced CO 2 levels. During these FACE experiments, elevated CO 2 was found to fertilize plant primary production, leading, for example, to yield increases for cereals [3] and grapevine [4] as well as increased litter production in forests [5]. Due to the usually short duration of FACE experiments, it remains unclear whether these effects are permanent. Nutrients such as nitrogen (N), for example, have been hypothesized to become progressively limited in relation to increased C input via CO 2 fertilization [6]. Reliable predictions are made difficult both by a lack of process understanding of the C-N interactions [7] and by the low general validity of hypotheses on the effect of increased CO 2 [8]. Process-based ecosystem models used for hypothesis testing are therefore required to include a range of effects, e.g., on decomposition by soil bacteria [9], soil respiration and root biomass [10], root exudation [11], and root-associated mycorrhizal fungi [12].However, translating these processes into a reliable projection of the ecosystem response to enhanced CO 2 by means of a set of mathematical equations is challenging. The various approaches include models that concentrate, for example, on the factors directly relevant to greenhouse gas emissions [13][14][15] or tr...