Integrated textural and geochemical analysis of igneous zircon by atom probe tomography

Mechanisms relating to growth and/or compositional modification of zircon occur at the atomic scale. For felsic igneous systems, processes responsible for growth patterns in zircon have previously remained elusive as the volume of material needed to analyze these compositional features using traditional in-situ methods is considerably larger than the typical sub-micron scale distribution of trace elements. To illuminate some of these driving forces, we characterize and quantify minor and trace element concentrations in igneous zircon grains by combining methods of cathodoluminescence (CL) imaging, electron microprobe microanalysis (EMPA) elemental maps for Hf, Y, Yb and U or Th, and atom probe tomography (APT). We focus on igneous zircon from the Chon Aike Silicic Large Igneous Province (Patagonia) that provide novel insights into (1) dissolution and re-crystallization during crustal anatexis, (2) crystallization to produce oscillatory zonation patterns that are typical of igneous zircons, and (3) the incorporation of trace element impurities (e.g., P, Be, and Al) at the nanoscale. Significantly, these APT volumes provide nanoscale sampling of boundaries between oscillatory growth zones in an igneous zircon to reveal compositional zoning of Y and, to a lesser extent P, which appear as high-angle, planar features. These concentration boundaries measured on the order of 10 to 12 nm are difficult to reconcile with proposed mechanisms for generating fine-scaled oscillations. Lastly, we fit diffusional profiles to measured Y concentrations to provide an estimate on the maximum timescales of zircon growth prior to eruption, as a function of the temperature at which diffusion occurred. When combined with known pressure-temperature-time paths for the magmatic system considered, these extremely short diffusion profiles that are resolvable by APT provide a powerful method to constrain timescales of crystal growth.