Changes in Silicic Melt Structure Between the Two Bandelier Caldera-Forming Eruptions, New Mexico, USA: Evidence from Zirconium and Light Rare Earth Elements

The Cerro Toledo Rhyolite is a group of high-silica rhyolitedomes and tephras which were erupted during the period betweenthe Lower Bandelier Tuff (LBT) at 1?45 Ma and the Upper BandelierTuff (UBT) at 1?12 Ma. The tephra sequence reflects the changingcomposition of the most fractionated liquids at the top of themagma chamber or chambers owing to crystallization during this0?33-Ma interval, over which it is possible to trace magma evolutionin detail. Incompatible elements such as Cs and Lu generallyincrease in concentration upsection through the tephra sequence.By contrast, Zr initially decreases upsection from 153 ppm to134 ppm in the middle, then increases upward to 320 ppm in themost evolved rhyolites. The Zr/Cs and Hf/Cs ratios initiallydecline, then become constant. The dramatic rise in Zr at nearlyconstant Zr/Cs suggests suppression of zircon crystallizationand a change from a high degree of zircon oversaturation toone of marginal oversaturation in the most evolved magmas. Theobserved Zr trends in the Cerro Toledo Rhyolite are oppositeto those (1) predicted by experimental studics of Zr solubilityin silicic magmas and (2) observed in the Bishop Tuff. LREEshow broadly similar relations to Zr and Hf. We have examined two parameters—iron content and volatilecontent of the magma—which may have controlled the crystallizationbehavior of zircon and the LREE-rich phase(s). The dramaticincrease in Zr and LREE in the most evolved Cerro Toledo Rhyolitesand basal UBT plinian tephras is accompanied by similar increasesin iron and halogen contents. If changa in the halogen contentsof matrix glasses are indicative of changes in overall volatilelevels at the top of the magma chamber(s), the increase in volatilesand iron may have modified the structural state of the magmaand increased the solubilities of zircon and the LREE-rich phase(s),thereby raising the saturation levels of Zr and LREE and stabilizingthese elements in the melt. Disruption of the melt structuremay have resulted from (1) Fe as a network modifier or quasi-molecularcomplex, (2) breaking of bridging oxygens by anions such asOH^– and F^–, and/or (3) complexing of Al and alkalisby OH, F, and/or Cl.