In the present investigation, a study was undertaken to understand the origin of Fe-minerals presents in Brazilian coal mining and to understand the environmental implication and the chemical heterogeneity in the study area. Coal cleaning residue samples rich in clays, quartz, sulphides, carbonates, sulphates, etc. were sampled from Lauro Muller, Urussanga, Treviso, Siderópolis, and Criciúma cities in the Santa Catarina State and a total of 19 samples were collected and Mössbauer, XRD, SEM/EDX, and TEM analyses were conducted on the samples. The major Fe-minerals identified are represented by the major minerals chlorite, hematite, illite, and pyrite, while the minor minerals include, ankerite, chalcopyrite, goethite, hematite, jarosite, maghemite, magnetie, marcasite, melanterite, natrojarosite, oligonite, pyrrhotite, rozenite, schwertmannite, siderite, and sideronatrile. Pyrite is relatively abundant in some cases, making up to around 10% of the mineral matter in several samples. The sulphates minerals such as jarosite and others, probably represent oxidation products of pyrite, developed during exposure or storage.