Rare Earth Element Mobility and Sr Isotope Systematics of Altered Volcanic Rocks from Seawater-Based and Magmatically-Influenced Hydrothermal Systems: Brothers Volcano, Kermadec Arc (IODP Expedition 376)

In 2018, International Ocean Discovery Program (IODP) Expedition 376 successfully drilled into seawater-based and magmatically-influenced hydrothermal systems within and on the wall of the caldera of Brothers volcano, an active submarine volcano in the Kermadec arc. We report rare earth element (REE) abundances and ratios for altered volcanic material recovered from three holes to assess mobility and partitioning under the different conditions of fluid-rock reactions. We combine these with loss on ignition (LOI) and X-ray diffraction (XRD) data to document the extent of alteration, and with Sr concentration and isotope data to evaluate water/rock (W/RSr) ratios and provide constraints on hydrothermal exchange and conditions of alteration. Rocks recovered from the seawater-based NW Caldera hydrothermal system show variable extents of alteration (LOI values of 1–11 wt %) at low W/RSr ratios (1–14) to chlorite- and quartz-rich alteration mineral assemblages. We attribute the limited changes observed in total REE content (ΣREE) and chondrite-normalized REE patterns to a combination of their incorporation into secondary minerals such as chlorite and smectite and complexation with chloride ligands in the reacting fluids. Rocks recovered from the magmatically-influenced Upper Cone hydrothermal field (and from an older interval deep beneath the NW Caldera wall) are more extensively altered (LOI values of 4 to >22 wt %), although at similar low W/RSr ratios (~1–16) to heterogeneous natroalunite- and pyrophyllite-bearing assemblages. The REEs exhibit considerably greater mobility with lower ΣREE contents, particularly in the middle and heavy REEs (LaN/YbN ratios up to 4). We suggest that accommodation in secondary minerals is unlikely to play a role in REE behavior due to their lack of substitution sites for the REEs. We attribute enhanced mobility of all the REEs to increased solubility due to the very low pH, and fractionation of the middle and heavy REEs as likely due to complexation with fluoride which enhances their solubility relative to the light REEs.