Lignite is a rich source of humic substances such as humic and fulvic acids that are natural chelating agents with multifold applications in fields ranging from agriculture to biomedicine. Associations of heterogeneous molecular components constitute to their complex and still unresolved structure. In this work we utilize X-band electron paramagnetic resonance (EPR) spectroscopy to characterize Fe3+ and Mn2+ complexation sites in fulvic acid (FA) extracted from lignite. EPR signals of FA-Fe3+ and FA-Mn2+ complexes are identified and investigated in detail under various conditions by the means of a newly developed program code and associated analysis method that yields an accurate description of the low-field (g(eff) approximate to 10-3) range EPR signal by assuming discrete distributions in the axial (D) and rhombic (lambda) zero field splitting (ZFS) parameters associated with Fe3+ complexation sites. The results refer to the presence of FA-Fe3+ complex structures with either low (vertical bar D vertical bar approximate to 0.26 cm(-1)) or high (vertical bar D vertical bar >= 1.0 cm(-1)) axial ZFS parameters along with a broad distribution in lambda. Outer-sphere, [Fe(OH2)(6)](3+) based complexes are found to be characterized with lambda = 1/3 along with lower axial ZFS values, in accordance with a distorted octahedral ligand configuration.