Geochemical evolution of a composite pluton: insight from major and trace element chemistry of titanite

Titanite from various rocks of the Karkonosze granitoid pluton (South-Eastern Poland) was studied, in order to evaluate its precision in recording magma evolution processes. The rocks are of lamprophyric, dioritic, granodioritic and granitic composition, including hybrid structures such as microgranular magmatic enclaves and composite dykes. Based on textures, chemistry and Zr-in-titanite geothermometry, titanites can be divided into magmatic and post-magmatic populations. Late- to post-magmatic titanite is present in almost all rock types, especially in the most evolved ones (where magmatic titanite is absent) and can be characterized by low trace element and high Al and F contents. Magmatic titanite crystallized in temperatures between 610 and 870 °C, after apatite and relatively simultaneously with amphibole and zircon. Titanite from lamprophyre exhibits compositional features typical of titanites formed in mafic rocks: low Al and F, high Ti4+/(Al + Fe3+), LREE (light rare earth elemet)-enriched chondrite-normalized REE patterns, low Y/Zr, Nb/Zr, Lu/Hf, high (Ce + Nd)/Y, Th/U and Zr. Titanite from hybrid rocks inherited these characteristics, indicating major contribution of the mantle-derived magma especially during early stages of magmatic evolution. Titanite compositional variations, as well as a wide range of crystallization temperatures in hybrid granodiorites point to prolonged crystallization from distinct magma domains of variable mafic versus felsic melt proportions. The extent of compositional variations decreases through subsequent stages of magmatic evolution, and titanite with the least contribution of the mafic component is characterized by higher total REE, Al and F contents, lower Ti4+/(Al + Fe3+), (Ce + Nd)/Y and Th/U ratios, LREE-depleted chondrite-normalized REE patterns and higher Y/Zr, Nb/Zr and Lu/Hf ratios. Titanite composition from the intermediate and late stage hybrids bears signature of decreasing amount of the mafic melt and higher degree of its evolution, however, the exact distinction between the former and the latter is very limited.