Ce and Eu anomalies in zircon as indicators of oxygen fugacity in subsolidus systems

Abstract

<p>Quantifying the oxygen fugacity (<i>f</i>o₂) of high temperature lithospheric fluids, including hydrothermal systems, presents a challenge because these fluids are difficult to capture and measure in the same manner as quenched glasses of silicate melts. The chemical properties of fluids can however be inferred through mineral proxies that interacted with the fluids through precipitation or recrystallization. Here, we present hydrothermal experiments to quantify the partition coefficients of rare earth elements (REEs) – including redox-sensitive Ce and Eu – between zircon and fluid. Experiments were conducted in a piston cylinder device at temperatures that range from 1200 to 800 °C under <i>f</i>o₂-buffered conditions in a SiO₂-ZrO₂-NaCl-REE-oxide system, and similar experiments were performed in the absence of NaCl (31 total experiments). The <i>f</i>o₂ was buffered to values that range from approximately 3 log units below to 7 log units above the fayalite magnetite quartz equilibrium. Zircon REE concentrations were quantified using laser ablation inductively coupled plasma mass spectrometry whereas the quenched fluids were extracted and measured by solution-based inductively coupled plasma mass spectrometry.</p>