Ferropyrosmalite-bearing fluid inclusions in the North Patagonian Andes metasedimentary basement, Argentina: A record of regional metasomatism

Abstract

AbstractQuartz segregations in paragneisses from the Paleozoic basement of the North Patagonian Andes contain highly saline multiphase fluid inclusions with the rare daughter mineral ferropyrosmalite detected by Raman analysis, besides halite, sylvite, hematite, and/or magnetite. During heating experiments, L-V homogenization occurs (256–515 °C), followed by halite dissolution (287–556 °C) and the dissolution of ferropyrosmalite at 550–581 °C. The latter phase transition triggers the growth of clinoamphibole crystals according to the following idealized reactions, written for potential end-members:4 F e 8 S i 6 O 15 [ ( O H ) 6 C l 4 ] + 6 C a 2 + ( a q ) Ferropyrosmalite ↔ 3 C a 2 F e 5 S i 8 ↔ O 22 ( O H ) 2 + 17 F e 2 + ( a q ) + 16 C l − ( a q ) + 12 O H − + 3 H 2 Ferro-actinolite F e 8 S i 6 O 15 [ ( O H ) 6 C l 4 ] + 2 C a 2 + ( a q ) Ferropyrosmalite + Fe 3 + ( aq ) + 2Al 3 + ( aq ) + Na + ( aq ) + H 2 O ↔ Na C a 2 ( Fe 4 2 + F e 3 + ) ( Al 2 Si 6 ) ↔ O 22 Cl 2 + 4 F e 2 + ( a q ) + 2 C l − ( a q ) + 4 H 2 Chloro-hastingsiteFerropyrosmalite ↔ Chloro-hastingsite The amphibole resembles the composition of ferro-actinolite but also has striking similarities with chloro-hastingsite, as indicated by Raman spectroscopy. During the heating experiment, hematite (when present) transforms to magnetite by the uptake of H2, whereas inclusions without Fe-oxides contain traces of H2 after the reaction. This mineral transformation shows that ferropyrosmalite might result from the retrograde re-equilibration of amphibole with the brine, implying the uptake of Fe2+, Cl–, and H2O and the enrichment of Ca2+ in the brine. Pervasive fluid flow and fluid-assisted diffusion are recorded by channel way microstructures, healed microfractures, and dissolution-reprecipitation phenomena, as demonstrated by cathodoluminescence microscopy. These alkali- and FeCl2-rich brines, derived from magmatic sources and of possible Mesozoic age, were related to regional metasomatism, coeval with widespread granitoid activity.