Rhenium and chalcophile elements in basaltic glasses from Ko'olau and Moloka'i volcanoes: Magmatic outgassing and composition of the Hawaiian plume

The behavior of chalcophile metals in volcanic environments is important for a variety of economic and environmental applications, and for understanding large-scale processes such as crustal recycling into the mantle. In order to better define the behavior of chalcophile metals in ocean island volcanoes, we measured the concentrations of Re, Cd, Bi, Cu, Pb, Zn, Pt, S, and a suite of major elements and lithophile trace elements in moderately evolved (6-7% MgO) tholeiitic glasses from Ko'olau and Moloka'i volcanoes. Correlated variations in the Re, Cd, and S contents of these glasses are consistent with loss of these elements as volatile species during magmatic outgassing. Bismuth also shows a good correlation with S in the Ko'olau glasses, but undegassed glasses from Moloka'i have unexpectedly low Bi contents. Rhenium appears to have been more volatile than either Cd or Bi in these magmas. Undegassed glasses with 880-1400 ppm S have 1.2-1.5 ppb Re and 130-145 ppb Cd. In contrast, outgassed melts with low S (<200 ppm) are depleted in these elements by factors of 2-5. Key ratios such as Re/Yb and Cu/Re are fractionated significantly from mantle values. Copper, Pb, and Pt contents of these glasses show no correlation with S, ruling out segregation of an immiscible magmatic sulfide phase as the cause of these variations. Undegassed Hawaiian tholeiites have Re/Yb ratios significantly higher than those of MORB, and extend to values greater than that of the primitive mantle. Loss of Re during outgassing of ocean island volcanoes, may help resolve the apparent paradox of low Re/Os ratios in ocean island basalts with radiogenic Os isotopic compositions. Plume source regions with Re/Yb ratios greater than that of the primitive mantle may provide at least a partial solution to the "missing Re" problem in which one or more reservoirs with high Re/Yb are required to balance the low Re/Yb of MORB.Lithophile trace element compositions of most Ko'olau and Moloka'i tholeiites are consistent with variable degrees of melting of fertile mantle peridotite. However, light rare earth element (LREE)-enriched glasses have trace element compositions more consistent with a garnet-rich source having a distinctive trace element composition. This provides additional evidence for a unique source component possibly related to recycled oceanic crust contributing to Ko'olau tholeiites.