The trace elemental and isotopic signatures in apatite can be modified during hydrothermal alteration. This study investigates the suitability of apatite as an indicator of the source, chemistry, and evolution of magma and hydrothermal fluids. In situ textural, elemental, and O-Sr-Nd isotope analyses were performed on apatite in thin sections, from fresh and propylitically altered pre- and synmineralized dioritic porphyries from the Black Mountain porphyry Cu deposit in the Philippines.

All studied apatite crystals have similar subhedral to euhedral shapes and are homogeneous in the grayscale in backscattered electron images. In cathodoluminescence images, the apatite in fresh and altered rocks displays yellow to yellow-green and green to brown luminescence, respectively. Apatite in fresh rocks has a higher Cl and Mn content, and lower Fe, Mg, Sr, Pb, and calculated XOH-apatite, compared to apatite in altered rocks. The content of F, rare earth elements (REEs), Y, U, Th, and Zr, and the Sr-Nd isotope signatures of apatite from fresh and altered rocks are similar in all apatite grains (87Sr/86Sr = 0.7034–0.7042 vs. 0.7032–0.7043, εNd(t) = 5.3–8.0 vs. 5.1–8.4). The X-ray maps and elemental and oxygen isotope signatures across individual apatite crystals are typically homogeneous in apatite from both fresh and altered rocks. The distinct luminescence colors, coupled with distinct mobile element compositions (Cl, OH, Mn, Mg, Fe, Sr, Pb), indicate modification of primary magmatic apatite during interaction with hydrothermal fluids. The similarities in Sr isotope ratios (87Sr/86Sr = 0.7032–0.7043) but slight differences in O isotope signatures (δ18O = 6.0 ± 0.3‰ vs. 6.6 ± 0.3‰) in apatite from fresh and altered rocks are consistent with the magma and hydrothermal fluids having the same source and suggest significant phase separation in the hydrothermal fluids given that 18O preferentially fractionates into the residual liquid relative to 16O during phase separation. The similarity of immobile element (REE, Y, U, Th, and Zr) contents in both populations of apatite, consistency of textures and Nd isotope compositions, and absence of obvious dissolution-reprecipitation features all suggest that altered apatite retains some magmatic characteristics. The apatite in fresh rocks has oxygen isotope compositions similar to that of zircons from the same sample (δ18O = 5.9 ± 0.3‰), indicating little to no oxygen isotope fractionation between zircon and apatite and that apatite can be a good proxy for the oxygen isotope composition of the magma. Based on the Cl contents of the magmatic and replacement apatite, and assuming their equilibrium with high-temperature magma fluid and replacement hydrothermal fluid, respectively, the calculated Cl content of the early magmatic fluid and the later replacement fluid can be estimated to be 6.4 to 15.1 wt % and ~0.25 ± 0.03 wt %, respectively. This indicates a depletion of Cl from the early high-temperature fluid to the replacement fluid, consistent with phase separation.

This study demonstrates that cathodoluminescence, elemental compositions (such as Cl, Mn, Mg, Fe, Sr, Pb) and Sr-O isotope signatures in apatite can be modified during hydrothermal alteration, whereas other components (REE, Y, U, Th, and Zr) and the Nd isotope composition are preserved. These features can be used to constrain the origin, chemistry, and evolution of the primary magma and ore-forming hydrothermal fluids.

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