Zircon trace element chemistry at sub-micrometer resolution for Tarawera volcano,New Zealand,and implications for rhyolite magma evolution

Zoned crystals can be important recorders of magmatic processes in space and time. However, in most situations, the temporal dimension is difficult to quantify. Here, we have employed secondary ion mass spectrometry depth profiling to excavate parallel pits into non-polished crystal faces of zircon to obtain ~5 μm resolution U–Th disequilibrium ages (one pit) that can be correlated with trace element zoning at sub-μm resolution derived from a second pit. Data from 17 crystals representing each of the four rhyolite eruptions of Tarawera volcano, an intra-caldera edifice within the Okataina Volcanic Centre, reveal diverse zircon growth conditions over time. Most crystals display rimward depletions in Zr/Hf and Ti, broadly consistent with cooling and crystallization. However, a significant fraction of crystals lacks these patterns and displays rimward trace element variations consistent with isothermal or prograde crystallization. Oscillatory zonation patterns in Y, Th, and U are superimposed on the Zr/Hf and Ti trends. Despite the limited number of crystals analyzed in this way, the striking lack of ubiquitous trace element zoning patterns in crystals from the same hand sample implies that fractional crystallization upon cooling was punctuated by magma recharge and crystal mixing affecting different parts of the magma reservoir. By combining data from all crystals, a systematic change to more heterogeneous trace element abundances is revealed by zircon crystal domains <45 ka following the Rotoiti caldera-forming eruption. This contrasts with the more uniform conditions of zircon crystallization lasting >100 ka prior to caldera formation and is best explained by the post-caldera system consisting of small, isolated melt pockets that evolved independently. An important conclusion is that the zircon ‘cargo’ in volcanic rocks reflects thermally and compositionally divergent processes that act near simultaneously in a magma storage region and not exclusively the conditions in the eruptible magma.