The retrograde hydration of the continental granitoid crust as seen from epidote-bearing veins: Trace elements and microstructures

The widespread presence of epidote-bearing veins and hydrous minerals such as micas in meta-granitoid rocks attests to the large extent of hydration of the exhuming continental crust. The ability of epidote (Ca₂Al₃Si₃O₁₂(OH) – Ca₂Al₂Fe³⁺Si₃O₁₂(OH)) to incorporate a wide variety of trace elements renders this mineral a promising geochemical tracer of circulating fluid(s).

We report trace element and microstructural data on epidote-bearing veins from the Aar Massif (Central Alps) and from the Albula Pass (Eastern Alps). We characterized and classified the epidote-bearing veins based on their extent of deformation, shape and size of the epidote grains, coexisting minerals, and degree of dynamic recrystallization of associated quartz. Laser ablation ICP-MS data of individual epidote crystals reveal prominent zoning, confirmed by electron probe maps for Sr and Mn. Overall, low to very low Th/U ratios (down to 0.0005 in the Aar Massif veins and 0.001 in the Albula ones) with Th often below limits of detection (< 0.1 µg/g at 16 µm beam size) go along with variably LREE-depleted patterns (and CI Chondrite-normalized La_N/Yb_N ~0.35 in the Aar Massif veins and ~0.60 in the Albula Pass veins). Strontium contents are variable (hundreds to thousands of µg/g) and mostly high (up to 10100 µg/g in the Aar Massif samples and 12800 µg/g in the Albula Pass samples). The in-situ geochemical data are linked to the microstructures in order to assess whether microstructures can be related to variations in trace elements, also considering the role of coexisting phases. Moreover, trace element data of samples from the Aar Massif are compared to metamorphic host-rock epidotes and cleft epidotes from the same massif.

We find that REE patterns of Aar Massif vein epidotes are clearly different than those of metamorphic host-rock epidotes and of cleft epidotes. In addition, REE patterns vary based on the microstructural characteristics of veins. Overall REE patterns of the Albula Pass vein epidotes resemble those from the Aar Massif. Different veins and microstructures define clusters in Sr vs. Y, Eu anomaly vs. Th/U ratios, and Eu anomaly vs. U values. Geochemical heterogeneities are observed among sampling localities within the Aar Massif.

The fact that the geochemical characteristics of retrograde hydrothermal vein epidotes are clearly different than those of high-grade metamorphic and metamorphic host-rock epidotes, and the relationship between geochemical characteristics and microstructures support the hypothesis that the deformation did not alter the original geochemical record through neomineralization. Our data argue for the potential of epidote as a powerful fluid tracer in the granitoid continental crust.