Dissolution Mediated Boron and Carbon Storage during Exhumation of HP Metapelites: Examples from New Hampshire Tourmaline-Graphite Intergrowths

The dynamic of light elements (e.g. C,B) in subduction zones is a complex process ultimately governed by variables such as P, T, fH₂ and pH. Interface phenomena at scales from the outcrop to intergranular surfaces play key chemical and mechanical roles on this dynamic (e.g. Galvez et al. 2013). We report here a petrological study of hydrated borosilicate tourmaline intergrown with graphite formed at the contact between igneous intrusives and high grade micaschists in New Hampshire graphite deposits (Rumble and Hoering, 1986). Our study includes Raman scattering, SEM, microprobe analysis and thermodynamic modeling, focusing on the Franklin Pierce and Walpole outcrops. Both localities experienced HP-HT metamorphism during the Acadian orogeny as well as complex metasomatic process during exhumation. The tourmaline-graphite intergrowths are structurally localized at and around contacts between an aplite sill and micaschists - biotite-muscovite-garnet-sillimanite-plagioclase-quartz-ilmenite - (Franklin Pierce), or along shear zones (Walpole) in veins. Tourmalines are dravitic in composition (i.e. Na, Mg rich with minor vacancy and Li content 0.2/0.1 a.p.f.u) and contain multiple primary tubular mixed fluid-solid inclusions containing graphite, quartz and gaseous CO₂ and CH₄. Sharp optical and compositional radial zonations are observed from core to rim in sections along and perpendicular to the c-axis. Blue-green cores are enriched in Mg and Ca (1.5/0.1 a.p.f.u respectively) whereas rims are enriched in Fe, Na and Ti (0.9/0.6/0.1 a.p.f.u respectively). Alternative interpretations in terms of sector zoning or compositional variability of the mineralizing fluid will be discussed. The carbonaceous material (CM) occurs primarily as flakes directly replacing biotite present in wall rocks. The structural ordering of CM, of unambiguous abiotic origin, reveals a material possessing the 3 dimensional structure of hexagonal graphite. Our results are critically compared to measurements done on other metasomatic or biogenic graphite displaying high structural ordering. Other textural habit of graphite are radiating crystals of graphite preferentially growing along crystalline planes of wall rock minerals (e.g. plagioclases) and at the interface between grain edge. We test whether a C and B(OH)₃^° (×As, Cu) rich acidic vapor unmixing from a salt-rich aqueous fluid exsolved from crystallizing igneous bodies can account for some geochemical and textural greisen-type metasomatic features of these outcrops. Other mechanical and geochemical processes participating in the process will be discussed. This work is direct evidence that respeciation and/or fluid-rock interaction at varying P,T,fH₂,pH conditions of fluids during exhumation, as well as interaction between magmatic bodies and metasedimentary units play a key role in the cycling of light elements during exhumation. Rumble, D., III, and Hoering, T.C., 1986, Carbon isotope geochemistry of graphite vein deposits from New Hampshire, U.S.A: Geochimica et Cosmochimica Acta, v. 50, p. 1239-1247. Galvez ME, Beyssac O, Martinez I, Benzerara K, Chaduteau C, Malvoisin B, Malavieille J (2013) Graphite formation by carbonate reduction during subduction. Nature Geoscience 6 (6):473-477