Performance of TiO2-based materials is highly dependent on the electronic structure and local defect configurations. Hence, a thorough understanding of defects interaction plays a key role. In this study we report on the results from emission 57Fe Mössbauer Spectroscopy experiments, using dilute 57Mn implantation into pristine (TiO2) and hydrogenated anatase held at temperatures between 300-700 K. Results of the electronic structure and local environment are complemented with ab-initio calculations. Upon implantation both Fe2+ and Fe3+ are observed in pristine anatase, where the latter demonstrates the spin-lattice relaxation. The spectra obtained for hydrogenated anatase show no Fe3+ contribution, suggesting that hydrogen acts as a donor. Due to the low threshold, hydrogen diffuses out of the lattice. Thus showing a dynamic behavior on the time scale of the 57Fe 14.4 keV state. The surrounding …