Yttrium and REE mineralization in manganese pods occurring in bentonite deposits of the Eocene Texas coastal plain

Eocene-aged bentonite deposits in Gonzalez (Texas, USA) carrfy scattered manganese oxide-rich pods where rare earth element (REE) concentrations as high as 7800 ppm have been detected - 10 times greater than in the already enriched bentonite. This study investigated the nature of the association between REEs and Mn oxides as well as REE modes of occurrence in these pods, in order to understand the processes that mobilize and accumulate REEs in the low-temperature depositional environment of the Texas coastal plain. Embedded, polished blocks of Mn pods were analyzed by Scanning Electron Microscopy (SEM); sections were then extracted by the FIB liftout technique from regions bearing REEs for further analysis by Transmission Electron Microscopy (TEM). The SEM and TEM results revealed the presence of abundant yttrium phosphate nanoparticles identified as xenotime, forming large globular aggregates that reach a few microns in diameter; these xenotime aggregates also host trace concentrations of Zr, Dy, Er, Yb, and Ce. Further, rhabdophane nanoparticles were detected that host predominantly light REEs and Y. The relative proportions of REEs in rhabdophane vary between particles and show decoupling of Ce from other light REEs, suggesting oxidation from Ce (super 3+) to Ce (super 4+) . The REE enrichment of these Mn pods is due to extensive weathering along fractures cutting through the bentonite deposit that drove their remobilization and transport downward. At the base of the bentonite, where fractures terminate against the boundary with a cemented sandstone, changes in flow regime combined with gradual downward changes in fluid composition, prompted co-precipitation of Mn oxides and REE phosphates (xenotime and rhabdophane).