Magmatic-hydrothermal fluids and volatile metals in the Spirit Lake pluton and Margaret Cu-Mo porphyry system, SW Washington, USA

The halogen-bearing minerals tourmaline, amphibole, and biotite formed during magmatic-hydrothermal processes associated with the late-stage cooling of the Spirit Lake granitoid pluton (Mt. St. Helens, WA) and with the younger sulphide-mineralised rocks of the Margaret Cu-Mo porphyry deposit located entirely within the pluton. Major-and trace-element discrimination suggests that one tourmaline population crystallised from fractionated late-stage melt pockets in granodiorite-monzogranitic dykes of the pluton. These coarse, euhedral, oscillatory, and complexly sector-zoned uvite tourmalines span a limited range in Mg/(Mg + Fe) [Mg#] space (0.4-0.7 apfu) and show the highest Ti, Ca, F, Nb, and Ta contents, and low X-site vacancies (<0.1 apfu), suggesting slow, ordered crystallisation. Conversely, smaller, microcrystalline, pluton-related vein tourmalines show higher X-site vacancies (>0.6 apfu), lower Ca and F contents, and the highest Li, As, and HREE contents (>80 ppm Li, >1200 ppm As). This population appears to record direct, rapid crystallisation from magmatic +/- meteoric fluid(s) bearing the signature of the breakdown of primary feldspars and pyroxenes, with fluid exsolution from fractionated melt patches likely triggered by the formation of the previous generation of tourmaline. Mineralised porphyry deposit tourmaline compositions from the stockwork span a much larger range in Mg# space (0.05-0.9 apfu) and are almost entirely Ca-free. X-sites of these schorl tourmalines are dominated by Na or vacancies, and the Y-sites are strongly Fe enriched. The highest Mn and Zn concentrations (>4000 and >1000 ppm, respectively) potentially reflect the composition of mineralising fluids during ore deposition. A number of boron isotopic analyses yield predominantly heavy boron, but delta B-11 values range from -5.2 to 6.2 % and average 1.4 %. Whilst most plutonic tourmalines conform to reported a-and c-sector element partitioning models, those from the mineralised porphyry show large and variable sector fractionation differences, suggesting that external controls may also be important. Wider evidence for late-stage pervasive metasomatism by halogen-bearing exsolved fluid(s) is provided by the high Mg# (>70) secondary amphiboles and biotites from within the Spirit Lake pluton, where the amphiboles are clear replacement products of primary pyroxenes. Fluid halogen fugacity ratios calculated from the biotite compositions overlap with other global mineralised porphyry systems, despite not being immediately associated with sulphide ores. The evidence suggests complex fluid processes and the coincidental development of the mineralised porphyry system within the pluton. Heat, fluids, and metals were therefore likely supplied by a later phase of magmatism, unrelated to the consolidation of the main Spirit Lake granitoid. These new constraints on magmatic-hydrothermal fluid signatures have wider applicability to potentially tracing proximal barren and mineralised processes, and for distinguishing between formation mechanisms for primary and secondary halogen-bearing minerals.