Nb/Ta, Zr/Hf and REE fractionation in exotic pegmatite from the Keivy province, NW Russia, with implications for rare-metal mineralization in alkali feldspar granite systems

The White Tundra pegmatites are associated with the Keivy alkali feldspar granite complex in the Kola Peninsula, NW Russia. The host granites are aegirine-arfvedsonite, biotite-arfvedsonite and biotite-ferrohastingsite varieties, ranging compositionally from peralkaline through metaluminous to peraluminous. The pegmatites are remarkable for the diversity of the rare-metal mineralization. The inferred crystallization sequence of the main REE, HFSE and Ti minerals in the pegmatite is: zircon - fergusonite-(Y) - monazite-(Ce) - gadolinite-hingganite series - britholite-(Y) - astrophyllite - titanite - allanite-(Ce) - chevkinite-(Ce) - ilmenite - kainosite-(Y) - REE carbonates. The pegmatites show unusual parageneses indicating a transition of the mineral associations from agpaitic to miaskitic in the same body (e.g. zirconosilicate -> zircon; astrophyllite -> titanite). A number of minerals have anomalous minor element contents. Astrophyllite and some titanites have low (even < 1) Nb/Ta and Zr/Hf ratios that contrast with the overall geochemical environment (ratios >> 1); titanite with very high Y and HREE contents; elevated Sn, W and V contents in some titanosilicates; allanite-(Ce) with very high Ti contents coupled with low (less than stoichiometric) values of Al, suggesting a Ti -> Al substitution. Whole-rock compositions of the host granite show a steady decrease of Nb/Ta and Zr/Hf ratios in peralkaline through metaluminous to peraluminous types. Compositions of Ti minerals suggest that further fractionation of Nb-Ta, Zr-Hf and REE in the White Tundra exotic pegmatite and the crystallization of Ti minerals with anomalous compositions are due to a combination of several factors: assimilation by the primary magma (enriched in Zr, Nb, REE) of upper crustal lithologies enriched in Ta, Hf, LREE, W, Sn; consumption of significant amounts of Nb and Zr by early-crystallized pegmatitic fergusonite and zircon with Nb/Ta and Zr/Hf >> 1; transition of HFSE mineral assemblages in pegmatite from agpaitic to miaskitic with consequent lowering of Nb/Ta and Zr/Hf; crystallization of minerals in a low-temperature (hydrothermal) environment with changing F contents, that promoted a sporadic further decrease of Nb/Ta and Zr/Hf (to values < 1) and increase of Y + HREE. The implications of the fractionation mechanisms for ore-forming processes related to rare-metal granites are discussed.