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.

Allanite is one of the main rare earth elements (REE)-rich accessory minerals in composite dykes from the granitoid pluton of Karkonosze. These dykes differ in composition from the bulk of the pluton by elevated rare earth elements (REE), Y, Zr, and alkali contents, suggesting contribution of an additional component. Allanite exhibits complex alteration textures, which can be divided into two stages. The first stage is represented by allanite mantles, formed by fluid infiltration into previously crystallized magmatic allanite. These zones have low totals, are Ca-, Al-, Mg-, and light REE (LREE)-depleted, and Y-, heavy REE (HREE)-, Th-, Ti-, and alkali-enriched. The fractionation between LREE and HREE was caused by different mobility of complexes formed by these elements in aqueous fluids. The second stage includes recrystallized LREE-poor, Y-HREE-rich allanite with variable Ca, Al, Mg, and REE-fluorocarbonates. The alteration products from both stages demonstrate higher Fe³⁺/(Fe²⁺ + Fe³⁺) ratios and a negative Ce anomaly. These features point to the alkaline, low-temperature, and oxidized nature of the fluids. The differences in mobility and solubility of respective ligands show that the fluids from the first stage may have been dominated by Cl, whereas those of the second stage may have been dominated by F and CO₂ (and PO₄ in case of one sample). The inferred chemistry of the fluids resembles the overall geochemical signature of the composite dykes, indicating a major contribution of the hydrothermal processes to their geochemical evolution.

In this paper, zonation patterns of trace elements in fluorapatite are discussed that were visualized using four analytical techniques, namely back-scattered electrons (BSE) and cathodoluminescence (CL) imaging, electron probe micro-analysis (EPMA), and micro-proton-induced X-ray/gamma ray emission (μPIXE/μPIGE) mapping. Each method demonstrates the in-grain compositional variations in a slightly different way. Both BSE and CL provide qualitative data, and the internal textures are displayed in most detail. Additionally, CL points to specific elements enriched in certain growth zones. Qualitative EPMA maps show detailed zonation patterns for specific elements (with high spatial resolution), which are in general correspondence with the patterns observed in BSE and CL images. The μPIXE/μPIGE maps are fully quantitative and the detection limits are relatively low compared to EPMA mapping. In present spot measurements μPIXE demonstrates lower detection limits than EPMA, however, the latter could be considerably improved by extending the acquisition times. There is no significant overlap of REE (rare earth elements) peaks in the acquired μPIXE energy spectra, however, when multiple REEs are present with sufficiently high concentrations, peak deconvolution may pose some difficulties. Spatial resolution of μPIXE/μPIGE images is not sufficiently high to reflect minor textural features, which also result from the greater interaction depth of the proton beam. However, major growth zones are distinguishable. Even though each method has their advantages and limitations, when applied together, they provide an almost complete characterization of compositional variability in trace-element-bearing minerals.

The chemical composition of different rocks as well as volatile-bearing and volatile-free minerals has been used to assess the presence of fluids in the Closepet batholith and to estimate the intensity of the fluid–rock interactions. The data were processed using polytopic vector analysis (PVA). Additional data include measurements of water content in the structure of volatile-free minerals and an examination of growth textures. The composition of mineral domains indicated formation/transformation processes with common fluid–mineral interactions. In general, the results suggested that the processes occurred in a ternary system. Two end-members were likely magmas and the third was enriched in fluids. In contrast, analysis of the apatite domains indicated that they likely formed/transformed in a more complex, four-component system. This system was fluid-rich and included hybrid magma with a large mafic component. PVA implies that the fluids do not appear to come from one source, given their close affinity and partial association with mantle-derived fluids. A dynamic tectonic setting promoting heat influx and redistribution, and interaction of fluids suggests that the formation/transformation processes of minerals and rocks occurred in a hot-spot like environment.