Partial rehydration of tubular halloysite (7 Å) immersed in La(NO3)3 solution for 3 years and its implication for understanding REE occurrence in weathered crust elution-deposited rare earth ores

Abstract

Clay minerals are the main carriers of rare earth elements (REE) in weathered crust elution-deposited rare earth (WED-RE) ores. The clay mineral-water interface reaction is among the most important interactions controlling the aggregation and transportation of REE(III) ions. Yet long-term experiments of interactions between REE(III) ions and clay minerals are scarce in the literature. Here, two typical clay minerals that commonly occur in WED-RE ores, namely tubular halloysite (7 Å) and platy kaolinite, were immersed in a La solution for 3 consecutive years. The specimens' characteristics were systematically determined using X-ray diffraction (XRD), transmission electron microscope (TEM), infrared spectroscopy (IR), and X-ray photoelectron spectroscopy (XPS). The partial rehydration of tubular halloysite (7 Å) was observed, with the resulting rehydrated halloysite characterized by lattice fringes having d(001)-values of ~1.000 and 0.830 nm, whose distribution features demonstrated that the partial rehydration happened initially at the outermost layers of the halloysite (7 Å). By contrast, both the morphology and structure of kaolinite remained intact after its 3-year-long immersion in the La solution. For both immersed halloysite and kaolinite, the La existed as inner-sphere complexes, outer-sphere complexes, and hydroxide particles adsorbed on the surface of minerals. However, La(III) ions partially penetrated the interlayer of halloysite but did not enter that of kaolinite. Accordingly, the intercalation of La(III) in halloysite may facilitate the rehydration of halloysite (7 Å). These experimental results provide novel insight into the conditions for rehydrating tubular halloysite (7 Å), and indicate a new possible state of REE(III) in WED-RE ores, both of which help us to better understand the geochemical behavior of REE and clay minerals in WED-RE ores.