Multiscale processes controlling niobium mobility during supergene weathering

Abstract

Niobium (Nb) is one of the most immobile elements during supergene weathering, widely used for mass-balance calculations, despite elusive information on the mechanisms controlling its dynamics in the critical zone. Here, a multiscale approach, from weathering profile to atomic-scale, is developed to monitor Nb speciation along a thick (about 50 m) lateritic regolith formed over the Pitinga pluton (Amazonas, Brazil). In the A-type parent granite, Nb is mainly hosted in ilmenite (1.5–2 wt% Nb2O5) and, to a lesser extent, in rutile (2–3 wt% Nb2O5). A quantitative assessment of the average Nb speciation from the parent rock to the upper horizons has been carried out by combining spectroscopic and spatially-resolved chemical techniques. The contribution of Nb-bearing Ti oxides (2–6 wt% Nb2O5) and Fe oxides (0.1–0.3 wt% Nb2O5) in the average Nb speciation increases with the degree of weathering and reaches 80% in the most altered horizon. This unusual Nb speciation results from the nature of the primary Nb carriers, less resistant to weathering than common Nb ore minerals such as pyrochlore. X-ray absorption spectroscopy demonstrates that Nb released from the weathering of ilmenite substitutes for Fe and Ti in goethite and Ti oxides, respectively, providing atomic-scale evidence of the high affinity of Nb for these phases. Elemental mobility of Nb, Ta and Sn followed by geochemical mass-transfer calculations evidences lateral transport from Nb-Sn-enriched laterites developed over the surrounding Nb-enriched facies of the Pitinga granite to the studied profile. Elements such as Ti, Zr and Hf, often considered immobile, are leached or redistributed in the studied profile. Our results demonstrate Nb remobilization during intense weathering. Although Nb scavenging by secondary Fe and Ti oxides limits Nb mobility at the mineral scale, this work questions the unrestricted use of Nb as a chemical invariant during surficial alteration processes.