Distribution of trace elements including tellurium, gallium, indium, and select REE in sulfide chimneys from Brothers submarine volcano, Kermadec arc
Brothers volcano is a dacitic volcano located along the Kermadec arc, New Zealand, and hosts the NW Caldera hydrothermal vent field perched on part of the steep caldera walls. The field strikes for ~600 m between depths of 1550 and 1700 m and includes numerous, active, high-temperature (max 302°C) chimneys and even more dead, sulfide-rich spires. Chimney samples collected from Brothers show distinct mineralogical zonation reflecting gradients in oxidation state, temperature, and pH from the inner walls in contact with hydrothermal fluids through to the outer walls in contact with seawater. Minerals deposited from hotter fluids (e.g., chalcopyrite) are located in the interior of the chimneys and are surrounded by an external zone of minerals deposited by cooler fluids (e.g., sulfates, sphalerite). Four chimneys types are identified at Brothers volcano based on the relative proportions of chalcopyrite and sulfate layers, and the presence or absence of anhydrite. Two are Cu-rich, i.e., chalcopyrite-rich and chalcopyrite-bornite-rich chimneys, and two are Zn-rich, i.e., sphalerite-rich and sphalerite-chalcopyrite-rich. Barite and anhydrite are common to both Cu-rich chimney types whereas Zn-rich chimneys contain barite only. The main mineral phases in all the chimneys are anhydrite, barite, chalcopyrite, pyrite/marcasite, and sphalerite. Trace minerals include galena, covellite, tennantite, realgar, chalcocite, bornite, hematite, goethite, Pb-As sulfosalts, and Bi- or Au-tellurides. The vast majority of tellurides are Cu-rich chimney also contained native Te in a similar distribution as the tellurides. Whole rock geochemical analysis has determined the maximum concentration of trace elements and REE such as In (53.1 ppm), Ga (1870), Y (26), La (21.2), Ce (21), Sm (2.8), Gd (4), and Yb (3) in Brothers chimneys. To better understand the mineral associations and zonation of these and other trace elements within the chimney walls, we have undertaken element mapping on the four different chimneys types with both X-Ray fluorescence microscopy using synchrotron radiation and with Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICPMS). For example, in a chalcopyrite-rich chimney visibly laminated chalcopyrite in the interior contains bands of Co, Mo, Ag, Te, Au, and Bi, whereas In, La, Ce, Ga, and Y are concentrated in other mineral phases towards the exterior. Element mapping allows us to better understand the physico-chemical gradients within chimney walls, as well as metal sources and transportation, and depositional processes.