Ghosts of apatite past: Using hyperspectral cathodoluminescence and micro-geochemical data to reveal multi-generational apatite in the Gifford Creek carbonatite complex, Australia

Abstract

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Apatite can host significant levels of trace elements, including REE, within its crystal lattice, making it particularly useful for deciphering geological events and processes. This study employs hyperspectral cathodoluminescence (CL) and in situ microchemical techniques to identify and characterize various generations of apatite occurring in the phoscorites, carbonatites, and fenites of the Gifford Creek Carbonatite Complex (GCCC), Western Australia. Hyperspectral CL revealed that apatite crystals in all samples have complex internal zoning, including multiple distinct generations, with zones of relatively bright CL generally having more complex spectra compared to darker CL zones. Most of the CL spectra have prominent sharp peaks at ∼1.4 eV and ∼2.l eV as well as a broad peak between 2.3 eV and 3.5 eV. We relate these different peaks to individual REE activators and groups of activators, in particular Nd3+, Eu3+, Sm3+, and Ce3+.

Trace element analyses of apatite confirm the relative enrichment of REE in the CL brighter zones. Most apatite generations exhibit concave-down to sinusoidal REY patterns lacking Eu anomalies, but often feature distinct negative Y anomalies. The depletion in LREE is interpreted to be due to LREE sequestration into monazite, which is relatively abundant in most of the samples. Most apatite samples contain very low Si contents, but appreciable Na, so REE incorporation into apatite was primarily via a coupled substitution of REE + Na replacing 2Ca, which is consistent with the highly alkaline, low SiO2 environment under which the apatite formed. Based on the combined trace-element signatures and CL textures, we interpret the multiple generations of apatite to reflect magmatic growth from alkaline magmas followed by recrystallization during subsequent metamorphic/hydrothermal events. The notable exception is the apatite core domains from a fenite sample that contain relatively high Si and Mn contents, low Sr, and relatively HREE-enriched REY patterns with distinct negative Eu anomalies. This apatite is interpreted to be relict from the granitic precursor to fenitization.

The apatite samples also show systematic compositional variations across the GCCC, with apatite from phoscorite samples from the southeast part of the complex containing higher Sr, lower Gd/Ce, and lower λ3 values (normalized REE pattern inflections) compared to apatite from the northwest part of the complex. Recognition of these spatial variations in apatite compositions from the intra-grain micro-scale through to the district scale demonstrates the utility of combining advanced petrographic methods, such as hyperspectral CL, with micro-chemical analysis to reveal complex geological records preserved in apatite. As apatite is a common accessory mineral, these techniques may be more broadly applicable to igneous source tracing, understanding metamorphic and/or metasomatic processes, provenance studies from detrital mineral records, and studies of the evolution of ore systems.