The hydrothermally active Brothers volcano on the Kermadec arc, New Zealand, hosts two geochemically distinct hydrothermal systems within a single caldera. At the NW Caldera, metal-sulfide–rich black smoker spires form on the caldera wall. In contrast, Fe-rich crusts and native sulfur-rich chimneys occur at the resurgent central Upper Cone. Previous studies have revealed that the contrasting styles of hydrothermalism relate to the variable contribution of magmatic volatiles between these sites, with the Upper Cone experiencing relatively higher amounts of magmatic volatile influx. We present results of a study of the hydrothermal alteration within Brothers volcano based on core samples to a depth of 453 meters below sea floor (mbsf) from both the Upper Cone (Site U5128) and NW Caldera sites (Site U1527 and U1530), drilled by the International Ocean Discovery Program. The dacitic to rhyolitic breccias that make up the volcano are variably altered to alteration mineral assemblages consisting of chlorite + quartz, illite + pyrophyllite, natroalunite + pyrophyllite, and smectite-rich assemblages. The distribution and textures of the alteration minerals within and between different sites at Brothers volcano reflect variations in temperature, fluid pH, and fluid flux. We find that natroalunite only occurs at the Upper Cone, while alteration at the NW Caldera is more diverse and is characterized by both chlorite and pyrophyllite-rich alteration, indicating that seawater-derived hydrothermal fluids overprinted earlier magmatic volatile-influenced alteration. Our data indicate that in magmatic volatile-dominated systems, the alteration mineralogy transitions from natroalunite to pyrophyllite-rich with increasing age or maturity. This is accompanied by a distinct change in sample texture from dominantly bleached selvages to a more massive, equigranular texture.

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