Birdwing-Shaped REE Profiles and Nb/Ta, Hf/Sm Ratios in the Bondy Gneiss Complex, Grenville Province, Québec: Sensitive Geochemical Markers of Fossil Hydrothermal Systems in High-Grade Metamorphic Terrains

Chondrite-normalized rare earth elements (REEs) profiles and high field strength elements (HFSEs) in rocks and minerals represent important tracers of geological processes. Of these the birdwing-shaped profile with negatively-sloped light REE ((La/Sm)N >1), positively-sloped heavy REE ((Tb/Yb)N <1), and strong negative Eu anomalies is commonly associated with large-scale hydrothermal systems or granitic intrusions. In a different way, severe deviation of Nb/Ta, Hf/Sm ratios from those of chondrite may also indicate hydrothermal signatures in the rocks involved as these ratios are generally stable and chondritic in normal magmatism as a result of their nearly identical ionic radii and charge. In this study, we present a typical setting where birdwing-shaped REE profiles together with Nb/Ta, Hf/Sm ratios unusually higher than those of chondrite, are systematically developed in a series of garnetite, quartzofeldspathic gneiss, Fe- or Mg-rich aluminous gneiss, and sulfides and magnetite. These units and associated Cu-Au mineralization form a VHMS-style hydrothermal system in the granulite-facies 1.4 Ga -1.35 Ga volcano-plutonic, arc-related Bondy gneiss complex (BGC), western Grenville Province, Canada. Outside the recognized hydrothermal system of the BGC, such REE profiles are not observed. Instead the surrounding felsic and mafic gneisses display primary trace element characteristics of island-arc magmas, suggesting that granulitefacies metamorphism did not modify significantly the trace element signatures of the protoliths. Although magmatic fractionation of accessory minerals can produce birdwing-shaped profiles, it cannot explain the extreme fractionation of isovalent trace elements (Nb-Ta) and the high Zr content of the hydrothermal rocks. Neither is it compatible with the lack of significant Nd depletion that would normally incur during this process. Following our study, we demonstrate that F-rich fluid and mineral phases enriched in LREEs and HREEs respectively must have been involved in the main hydrothermal alteration and REE fractionation process in the BGC. Preferential removal of REEs from the interstitial glass of the volcanic protoliths together with dissolution of plagioclase and subsequent external influx of HREEs and HFSEs can produce birdwing-shaped REE profiles. In turn, such profiles and/or unusual Nb/Ta, Hf/Sm ratios can be used as a sensitive marker of hydrothermally altered rocks in targeting mineral exploration.