New insight into the origin of manganese oxide ore deposits in the Appalachian Valley and Ridge of northeastern Tennessee and northern Virginia, USA

Manganese oxide deposits have long been observed in association with carbonates within the Appalachian Mountains, but their origin has remained enigmatic for well over a century. Ore deposits of Mn oxides from several productive sites located in eastern Tennessee and northern Virginia display morphologies that include botryoidal and branching forms, massive nodules, breccia matrix cements, and fracture fills. The primary ore minerals include hollandite, cryptomelane, and romanèchite. Samples of Mn oxides from multiple localities in these regions were analyzed using electron microscopy, X-ray analysis, Fourier transform infrared spectroscopy, and trace and rare earth element (REE) geochemistry. The samples from eastern Tennessee have biological morphologies, contain residual biopolymers, and exhibit REE signatures that suggest the ore formation was due to supergene enrichment (likely coupled with microbial activity). In contrast, several northern Virginia ores hosted within quartz-sandstone breccias exhibit petrographic relations, mineral morphologies, and REE signatures indicating inorganic precipitation, and a likely hydrothermal origin with supergene overprinting. Nodular accumulations of Mn oxides within weathered alluvial deposits that occur close to breccia-hosted Mn deposits in Virginia show geochemical signatures that are distinct from the breccia matrices and appear to reflect remobilization of earlier-emplaced Mn and concentration within supergene traps. Based on the proximity of all of the productive ore deposits to mapped faults or other zones of deformation, we suggest that the primary source of all of the Mn may have been deep seated, and that Mn oxides with supergene and/or biological characteristics resulted from the local remobilization and concentration of this primary Mn.